TW583221B - Low molecular weight polyphenylene ether - Google Patents
Low molecular weight polyphenylene ether Download PDFInfo
- Publication number
- TW583221B TW583221B TW092104827A TW92104827A TW583221B TW 583221 B TW583221 B TW 583221B TW 092104827 A TW092104827 A TW 092104827A TW 92104827 A TW92104827 A TW 92104827A TW 583221 B TW583221 B TW 583221B
- Authority
- TW
- Taiwan
- Prior art keywords
- polyphenylene ether
- molecular weight
- low molecular
- solvent
- patent application
- Prior art date
Links
- 229920001955 polyphenylene ether Polymers 0.000 title claims abstract description 194
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 18
- 238000009826 distribution Methods 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims description 101
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 90
- 238000000034 method Methods 0.000 claims description 76
- 239000002245 particle Substances 0.000 claims description 53
- 238000006116 polymerization reaction Methods 0.000 claims description 53
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 45
- -1 phenol compound Chemical class 0.000 claims description 36
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 34
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 claims description 30
- 239000003054 catalyst Substances 0.000 claims description 29
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 21
- 229910052760 oxygen Inorganic materials 0.000 claims description 21
- 239000001301 oxygen Substances 0.000 claims description 21
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 150000001298 alcohols Chemical class 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 11
- 239000012046 mixed solvent Substances 0.000 claims description 11
- 239000005749 Copper compound Substances 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 150000001880 copper compounds Chemical class 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 9
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 2,3,6-Trimethylphenol Chemical compound CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- 150000002366 halogen compounds Chemical class 0.000 claims description 8
- 239000008096 xylene Substances 0.000 claims description 8
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 claims description 6
- 230000009477 glass transition Effects 0.000 claims description 6
- 125000003107 substituted aryl group Chemical group 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- ATGFTMUSEPZNJD-UHFFFAOYSA-N 2,6-diphenylphenol Chemical compound OC1=C(C=2C=CC=CC=2)C=CC=C1C1=CC=CC=C1 ATGFTMUSEPZNJD-UHFFFAOYSA-N 0.000 claims description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 125000005415 substituted alkoxy group Chemical group 0.000 claims description 4
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229940117389 dichlorobenzene Drugs 0.000 claims description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 239000005947 Dimethoate Substances 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- MCWXGJITAZMZEV-UHFFFAOYSA-N dimethoate Chemical compound CNC(=O)CSP(=S)(OC)OC MCWXGJITAZMZEV-UHFFFAOYSA-N 0.000 claims 1
- 229920006389 polyphenyl polymer Polymers 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 7
- 239000003607 modifier Substances 0.000 abstract description 4
- 239000002305 electric material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 31
- 229910052757 nitrogen Inorganic materials 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 16
- 238000005259 measurement Methods 0.000 description 14
- 238000007872 degassing Methods 0.000 description 10
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 150000002989 phenols Chemical class 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000012776 electronic material Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- IXQGCWUGDFDQMF-UHFFFAOYSA-N 2-Ethylphenol Chemical compound CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- CIRRFAQIWQFQSS-UHFFFAOYSA-N 6-ethyl-o-cresol Chemical compound CCC1=CC=CC(C)=C1O CIRRFAQIWQFQSS-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- DJEQZVQFEPKLOY-UHFFFAOYSA-N N,N-dimethylbutylamine Chemical compound CCCCN(C)C DJEQZVQFEPKLOY-UHFFFAOYSA-N 0.000 description 2
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 description 2
- QCOGKXLOEWLIDC-UHFFFAOYSA-N N-methylbutylamine Chemical compound CCCCNC QCOGKXLOEWLIDC-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 2
- 229940045803 cuprous chloride Drugs 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 description 2
- 239000012433 hydrogen halide Substances 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- RJCXIVJEQLXULD-UHFFFAOYSA-N n'-(2-methylpropyl)ethane-1,2-diamine Chemical compound CC(C)CNCCN RJCXIVJEQLXULD-UHFFFAOYSA-N 0.000 description 2
- DFPGBRPWDZFIPP-UHFFFAOYSA-N n'-butylethane-1,2-diamine Chemical compound CCCCNCCN DFPGBRPWDZFIPP-UHFFFAOYSA-N 0.000 description 2
- NLGKRVNANIZGNI-UHFFFAOYSA-N n,2,6-trimethylaniline Chemical compound CNC1=C(C)C=CC=C1C NLGKRVNANIZGNI-UHFFFAOYSA-N 0.000 description 2
- GVWISOJSERXQBM-UHFFFAOYSA-N n-methylpropan-1-amine Chemical compound CCCNC GVWISOJSERXQBM-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 230000037048 polymerization activity Effects 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000012673 precipitation polymerization Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical compound C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- XRUGBBIQLIVCSI-UHFFFAOYSA-N 2,3,4-trimethylphenol Chemical compound CC1=CC=C(O)C(C)=C1C XRUGBBIQLIVCSI-UHFFFAOYSA-N 0.000 description 1
- BPRYUXCVCCNUFE-UHFFFAOYSA-N 2,4,6-trimethylphenol Chemical compound CC1=CC(C)=C(O)C(C)=C1 BPRYUXCVCCNUFE-UHFFFAOYSA-N 0.000 description 1
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 description 1
- METWAQRCMRWDAW-UHFFFAOYSA-N 2,6-diethylphenol Chemical compound CCC1=CC=CC(CC)=C1O METWAQRCMRWDAW-UHFFFAOYSA-N 0.000 description 1
- NAILKKRDWBJCNH-UHFFFAOYSA-N 2,6-dipropylphenol Chemical compound CCCC1=CC=CC(CCC)=C1O NAILKKRDWBJCNH-UHFFFAOYSA-N 0.000 description 1
- MTUHNOQQFRNDBN-UHFFFAOYSA-N 2-(2,6-dimethylphenyl)phenol Chemical compound CC1=CC=CC(C)=C1C1=CC=CC=C1O MTUHNOQQFRNDBN-UHFFFAOYSA-N 0.000 description 1
- FRJSZCNBYVMOTD-UHFFFAOYSA-N 2-(4-chloroanilino)ethanol Chemical compound OCCNC1=CC=C(Cl)C=C1 FRJSZCNBYVMOTD-UHFFFAOYSA-N 0.000 description 1
- YVJVQYNIANZFFM-UHFFFAOYSA-N 2-(4-methylanilino)ethanol Chemical compound CC1=CC=C(NCCO)C=C1 YVJVQYNIANZFFM-UHFFFAOYSA-N 0.000 description 1
- MWGATWIBSKHFMR-UHFFFAOYSA-N 2-anilinoethanol Chemical compound OCCNC1=CC=CC=C1 MWGATWIBSKHFMR-UHFFFAOYSA-N 0.000 description 1
- KTIRRDOBTNZKNL-UHFFFAOYSA-N 2-bromo-6-ethylphenol Chemical compound CCC1=CC=CC(Br)=C1O KTIRRDOBTNZKNL-UHFFFAOYSA-N 0.000 description 1
- YXZPTVOCJLCMRO-UHFFFAOYSA-N 2-bromo-6-methylphenol Chemical compound CC1=CC=CC(Br)=C1O YXZPTVOCJLCMRO-UHFFFAOYSA-N 0.000 description 1
- KUNNUNBSGQSGDY-UHFFFAOYSA-N 2-butyl-6-methylphenol Chemical compound CCCCC1=CC=CC(C)=C1O KUNNUNBSGQSGDY-UHFFFAOYSA-N 0.000 description 1
- XNJCFOQHSHYSLG-UHFFFAOYSA-N 2-chloro-6-ethylphenol Chemical compound CCC1=CC=CC(Cl)=C1O XNJCFOQHSHYSLG-UHFFFAOYSA-N 0.000 description 1
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- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
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- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
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- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- WIVXEZIMDUGYRW-UHFFFAOYSA-L copper(i) sulfate Chemical compound [Cu+].[Cu+].[O-]S([O-])(=O)=O WIVXEZIMDUGYRW-UHFFFAOYSA-L 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
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- 150000004985 diamines Chemical class 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- LAWOZCWGWDVVSG-UHFFFAOYSA-N dioctylamine Chemical compound CCCCCCCCNCCCCCCCC LAWOZCWGWDVVSG-UHFFFAOYSA-N 0.000 description 1
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- 238000007599 discharging Methods 0.000 description 1
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- 150000004659 dithiocarbamates Chemical class 0.000 description 1
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- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
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- 229910052945 inorganic sulfide Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 description 1
- VMGAPWLDMVPYIA-HIDZBRGKSA-N n'-amino-n-iminomethanimidamide Chemical compound N\N=C\N=N VMGAPWLDMVPYIA-HIDZBRGKSA-N 0.000 description 1
- KFIGICHILYTCJF-UHFFFAOYSA-N n'-methylethane-1,2-diamine Chemical compound CNCCN KFIGICHILYTCJF-UHFFFAOYSA-N 0.000 description 1
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- KVKFRMCSXWQSNT-UHFFFAOYSA-N n,n'-dimethylethane-1,2-diamine Chemical compound CNCCNC KVKFRMCSXWQSNT-UHFFFAOYSA-N 0.000 description 1
- JWAJUTZQGZBKFS-UHFFFAOYSA-N n,n-diethylprop-2-en-1-amine Chemical compound CCN(CC)CC=C JWAJUTZQGZBKFS-UHFFFAOYSA-N 0.000 description 1
- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical compound CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 description 1
- ZUHZZVMEUAUWHY-UHFFFAOYSA-N n,n-dimethylpropan-1-amine Chemical compound CCCN(C)C ZUHZZVMEUAUWHY-UHFFFAOYSA-N 0.000 description 1
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- GMTCPFCMAHMEMT-UHFFFAOYSA-N n-decyldecan-1-amine Chemical compound CCCCCCCCCCNCCCCCCCCCC GMTCPFCMAHMEMT-UHFFFAOYSA-N 0.000 description 1
- PXSXRABJBXYMFT-UHFFFAOYSA-N n-hexylhexan-1-amine Chemical compound CCCCCCNCCCCCC PXSXRABJBXYMFT-UHFFFAOYSA-N 0.000 description 1
- CATWEXRJGNBIJD-UHFFFAOYSA-N n-tert-butyl-2-methylpropan-2-amine Chemical compound CC(C)(C)NC(C)(C)C CATWEXRJGNBIJD-UHFFFAOYSA-N 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 235000010292 orthophenyl phenol Nutrition 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229960000395 phenylpropanolamine Drugs 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- BOLDJAUMGUJJKM-LSDHHAIUSA-N renifolin D Natural products CC(=C)[C@@H]1Cc2c(O)c(O)ccc2[C@H]1CC(=O)c3ccc(O)cc3O BOLDJAUMGUJJKM-LSDHHAIUSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000001374 small-angle light scattering Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- UQFSVBXCNGCBBW-UHFFFAOYSA-M tetraethylammonium iodide Chemical compound [I-].CC[N+](CC)(CC)CC UQFSVBXCNGCBBW-UHFFFAOYSA-M 0.000 description 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
- RXMRGBVLCSYIBO-UHFFFAOYSA-M tetramethylazanium;iodide Chemical compound [I-].C[N+](C)(C)C RXMRGBVLCSYIBO-UHFFFAOYSA-M 0.000 description 1
- 125000004149 thio group Chemical group *S* 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/44—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols by oxidation of phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
- C08L71/123—Polyphenylene oxides not modified by chemical after-treatment
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0326—Organic insulating material consisting of one material containing O
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
Abstract
Description
583221 (1) 玖、發明說明 【發明所屬之技術領域】 本發明爲關於低分子量之聚苯醚。詳言之，爲關於耐 熱性、電氣特性及各種溶劑和對於試藥之溶解性優良，且 與其他成分之混合性、反應性優良之低分子量的聚苯醚。 更且，關於可有效率製造該低分子量聚苯醚之方法、及以 此方法所得之低分子量的聚苯醚。 【先前技術】 聚苯醚爲加工性、生產性優良，可經由熔融注射成形 法和熔融擠壓成形法等之成形方法，有效率生產出所欲形 狀之製品、構件，故廣泛使用做爲電氣、電子領域、汽車 領域 '其他各種工業材料領域、食品包裝領域之製品、構 件用之材料。 製造聚苯醚之方法已提案出特公昭3 6 - 1 8692號公報 、美國專利第 3 3 06 87 5號說明書、同3 344 1 1 6號、同 3432466號爲首的許多製法。 以此些公知方法所取得，且於上述用途中所用之聚苯 醚爲還原粘度0.3 dl/g以上的高分子量聚合物。但是， 最近’期待極低分子量之聚苯醚爲比通常的高分子量聚苯 醚，更有效用於印刷基板等之電子材料用途。近年，隨著 印刷基板等之電子材料的高集成化，使得配線本身的導體 損失被特寫放大，損失部分爲以熱型式釋出。因此，對於 印刷基板材料要求優良的低介電率特性及高耐熱性。又， -6 - (2) 於製造印刷基板之過程中，通常爲溶於溶劑中並且經由變 性反應令其官能化後，進行硬化等之反應。因此，對於溶 劑的溶解性和與其他成分之反應性優良亦爲必要的。 低分子量之聚苯醚被揭示於特公昭5 0 - 6 5 2 0號、特 開昭62— 39628號及美國專利6211327號等，且任一種方 法所得之低分子量聚苯醚亦均於耐熱性及電氣特性等方面 不能稱爲充分。 於特公昭5 〇 — 6 5 2 〇號公報中，揭示於苯、甲苯、二 甲苯等之芳香族烴類、與正己烷、異己烷、正庚烷等之脂 族烴類之混合溶劑中，製造聚苯醚之方法。但是，所得之 低分子量聚苯醚爲於耐熱性及電氣特性等方面並不能稱爲 充分，更且如實施例中所明白般，於還原粘度爲0.2 dl/ g以下之低分子量區域所得之低分子量聚苯醚爲經由附著 至反應容器等而發生產率降低的問題。 聚苯醚的聚合溶劑於使用聚苯醚之良溶劑（上述公報 中之苯、甲苯、二甲苯等之芳香族烴類）時，因爲該良溶 劑對於所得之聚苯醚的親和性爲良好，故不僅爲低分子量 附著至反應器令產率降低，且將良溶劑由聚苯醚中除去之 設備變成過大，具有對於設備之溫度控制不得不極爲神經 質等之問題點。因此，以良好效率所取得之低分子量聚苯 醚的還原粘度於現狀充其量停留於0.2 dl/ g附近。 特開昭62 - 3 9628號公報爲關於數平均分子量爲未滿 2 8 00之低分子量聚苯醚，且示出將碳數1〜5個之單官能 性醇類與視需要之水倂用做爲聚合溶劑之方法。但是所得 (3) (3)583221 之低分子量聚苯醚爲於耐熱性及電氣特性等方面並不能稱 爲充分，且產率僅取得9 5 %爲止（實際於實施例中爲未 滿90 % )，並且如實施例中所記載般具有聚合極耗費時 間之問題，且非爲工業上有效率的方法。 於美國專利第62 1 1 327號中，揭示由低分子量聚苯醚 之聚合溶液中除去水性相中的觸媒成分，其次由聚苯醚溶 液中直接將聚苯醚的良溶劑予以脫氣（例如使用脫氣擠壓 機等），製造低分子量聚苯醚之方法。此方法爲關於還原 粘度爲0.1 dl/g左右或以下之極低分子量之聚苯醚的製 造，雖爲完全無產率問題之經改良方法，但仍於耐熱性及 電氣特性等方面不能稱爲充分。 更且，此些方法所得之低分子量聚苯醚一般爲具有顆 粒狀或九狀之形態。因爲具有大粒子，故溶於溶劑時耗費 時間、並且成爲半溶解且附著至反應機構壁面等之麻煩的 原因。 【發明內容】 <發明之揭示> 本發明爲以提供耐熱性和電氣特性之優良，且對於溶 劑等之溶解性優良之低分子量的聚苯醚爲其目的。更且， 以提供有效率製造該低分子量聚苯醚之方法爲其目的。 本發明者等人爲了解決上述課題而進行致力檢討，並 且完成本發明。 即，本發明爲 -8 - (4) (4)583221 1. 一種低分子量聚苯醚，其特徵爲於30°C中以濃度 0.5 g / dl之氯仿溶液中測定之還原粘度爲〇.〇4〜0.18 dl/ g，分子量分佈爲1.5〜2.5、 2. 如上述1之低分子量聚苯醚，其中玻璃態化溫度 (Tg)爲以下式表示、583221 (1) 发明 Description of the invention [Technical field to which the invention belongs] The present invention relates to a low molecular weight polyphenylene ether. Specifically, it is a low-molecular-weight polyphenylene ether that is excellent in heat resistance, electrical characteristics, various solvents, and solubility in reagents, and has good miscibility and reactivity with other components. Furthermore, it relates to a method for efficiently producing the low molecular weight polyphenylene ether, and a low molecular weight polyphenylene ether obtained by this method. [Prior technology] Polyphenylene ether has excellent processability and productivity. It can be used to produce products and components of the desired shape through molding methods such as melt injection molding and melt extrusion molding. Therefore, it is widely used as electrical, Electronic field, automotive field, various other industrial material fields, food packaging field products, components for materials. Many methods of manufacturing polyphenylene ether have been proposed, including Japanese Patent Publication No. 3 6-1 8692, US Patent No. 3 3 06 87 5, and 3 344 1 16 and 3432466. The polyphenylene ethers obtained by these known methods and used in the above applications are high molecular weight polymers having a reduced viscosity of 0.3 dl / g or more. However, recently, polyphenylene ethers of extremely low molecular weight are expected to be more effectively used for electronic material applications such as printed circuit boards than ordinary high molecular weight polyphenylene ethers. In recent years, with the high integration of electronic materials such as printed circuit boards, the conductor loss of the wiring itself has been enlarged by close-ups, and the loss has been released in a thermal form. Therefore, excellent low dielectric constant characteristics and high heat resistance are required for printed circuit board materials. In addition, -6-(2) In the process of manufacturing a printed circuit board, it is usually dissolved in a solvent, functionalized by a modification reaction, and then subjected to a reaction such as hardening. Therefore, it is necessary to have excellent solubility in the solvent and reactivity with other components. Low-molecular-weight polyphenylene ethers are disclosed in JP-A No. 5 0-6 5 2 0, JP-A No. 62-39628, and US Patent No. 6211327, etc., and the low-molecular-weight polyphenylene ether obtained by any method is also heat resistant. And electrical characteristics cannot be called sufficient. In Japanese Patent Publication No. 5-60-6202, it is disclosed in a mixed solvent of aromatic hydrocarbons such as benzene, toluene and xylene, and aliphatic hydrocarbons such as n-hexane, isohexane, and n-heptane. Method for making polyphenylene ether. However, the obtained low-molecular-weight polyphenylene ether cannot be said to be sufficient in terms of heat resistance and electrical characteristics. Moreover, as is clear from the examples, the obtained low-molecular-weight polyphenylene ether has a low viscosity in a low-molecular weight region having a viscosity of 0.2 dl / g or less The molecular weight polyphenylene ether has a problem in that productivity decreases due to adhesion to a reaction vessel or the like. When a good solvent for polyphenylene ether is used as a good solvent for polyphenylene ether (aromatic hydrocarbons such as benzene, toluene, xylene, etc. in the above publication), the good solvent has good affinity for the obtained polyphenylene ether. Therefore, not only the low molecular weight is attached to the reactor to reduce the yield, but also the equipment for removing the good solvent from the polyphenylene ether becomes too large, which has the problem that the temperature control of the equipment must be extremely neurotic. Therefore, the reduced viscosity of the low-molecular-weight polyphenylene ether obtained with good efficiency stays at around 0.2 dl / g at best. Japanese Unexamined Patent Publication No. 62-3 9628 is a low-molecular-weight polyphenylene ether having a number average molecular weight of less than 2 800, and shows the use of monofunctional alcohols having 1 to 5 carbon atoms and water as needed. As a method of polymerization solvent. However, the obtained low-molecular-weight polyphenylene ether (3) (3) 583221 was not sufficient in terms of heat resistance and electrical characteristics, and the yield was only 95% (actually less than 90% in the examples). ), And as described in the examples, it has a problem of extremely time-consuming polymerization, and is not an industrially efficient method. In US Patent No. 62 1 1 327, it is disclosed that the catalyst component in the aqueous phase is removed from the polymerization solution of low molecular weight polyphenylene ether, and then the good solvent of polyphenylene ether is directly degassed from the polyphenylene ether solution ( For example, using a degassing extruder, etc.), a method for producing low molecular weight polyphenylene ether. This method is for the production of extremely low molecular weight polyphenylene ether with a reduced viscosity of about 0.1 dl / g or less. Although it is an improved method without any problem of yield, it cannot be said to be sufficient in terms of heat resistance and electrical characteristics. . Moreover, the low-molecular-weight polyphenylene ethers obtained by these methods generally have a granular or nine-shaped form. Since it has large particles, it takes time to dissolve in the solvent, and it causes troubles such as being semi-dissolved and adhering to the wall of the reaction mechanism. [Summary of the invention] < Disclosure of the invention > The present invention aims to provide a low-molecular-weight polyphenylene ether which is excellent in heat resistance and electrical characteristics and excellent in solubility to solvents and the like. Furthermore, it aims at providing the method of manufacturing this low molecular weight polyphenylene ether efficiently. The inventors of the present invention made an intensive review in order to solve the above problems, and completed the present invention. That is, the present invention is -8-(4) (4) 583221 1. A low molecular weight polyphenylene ether, characterized in that the reduced viscosity measured in a chloroform solution at a concentration of 0.5 g / dl at 30 ° C is 0.00. 4 ~ 0.18 dl / g, molecular weight distribution is 1.5 ~ 2.5, 2. Low molecular weight polyphenylene ether as in the above 1, wherein the glass transition temperature (Tg) is represented by the following formula,
Tg(〇C) > 600 X ( 7?sp/c] +105 3. —種聚苯醚粉末，其特徵爲由如上述1或2記載 之低分子量聚苯醚所構成、 4. 如上述3之聚苯醚粉末，其中平均粒徑爲5.0〜 1,000 // m ' 5. 如上述3之聚苯醚粉末，其中平均粒徑爲5.0〜 500 β m ' 6. 如上述3之聚苯醚粉末，其中平均粒徑爲5.0〜 3 00 // m、 7. 如上述3之聚苯醚粉末，其中平均粒徑爲5.0〜 1 0 0 // m、 8. 如上述3之聚苯醚粉末，其爲實質上不含有1,000 // m以上之粒子、 9. 如上述1之低分子量聚苯醚，其爲令苯酚化合物 於觸媒與含氧氣體存在下聚合取得、 10. 如上述9之低分子量聚苯醚，其中苯酚化合物爲 2，6—二甲基苯酚、 11. 如上述9之低分子量聚苯醚，其中苯酚化合物爲 2，6 —二甲基苯酚與2，3，6 —三甲基苯酚的混合物、 -9- (5)583221 12.如上述9之低分子量聚苯醚，其中苯酚化合物爲 2，6 - 一甲基苯酚與2，6 一二苯基酚的混合物、 13·如上述10〜12中任〜項之低分子量聚苯醚，其 中苯酣化合物爲再含有式（1)所示之二價苯酚、Tg (〇C) > 600 X (7? Sp / c) +105 3. A kind of polyphenylene ether powder, characterized by being composed of low molecular weight polyphenylene ether as described in 1 or 2 above, 4. as described above Polyphenylene ether powder of 3, wherein the average particle size is 5.0 ~ 1,000 // m '5. Polyphenylene ether powder of 3, wherein the average particle size is 5.0 ~ 500 β m' 6. Polyphenylene ether of 3, as described above Powder, where the average particle size is 5.0 ~ 3 00 // m, 7. polyphenylene ether powder as described in 3 above, where the average particle size is 5.0 ~ 1 0 0 // m, 8. polyphenylene ether powder as described in 3 above It is substantially free of particles of 1,000 // m or more. 9. The low molecular weight polyphenylene ether as in the above 1 is obtained by polymerizing a phenol compound in the presence of a catalyst and an oxygen-containing gas. 10. As in 9 of the above. Low molecular weight polyphenylene ether, in which the phenol compound is 2,6-dimethylphenol, 11. The low molecular weight polyphenylene ether in accordance with the above 9, wherein the phenol compound is 2,6-dimethylphenol and 2,3,6 — Mixture of trimethylphenol, -9- (5) 583221 12. Low molecular weight polyphenylene ether according to 9 above, wherein the phenol compound is a mixture of 2,6-monomethylphenol and 2,6-diphenylphenol 13. The low molecular weight polyphenylene ether according to any one of items 10 to 12 above, wherein the phenylhydrazone compound further contains a divalent phenol represented by formula (1),
(式中，Qi、Q2爲表示相同或相異之取代基，且表示氫 、烷基、經取代烷基、芳烷基、經取代芳烷基、芳基、經 取代方基、烷氧基、經取代烷氧基或鹵素，且分別可相同 或相異；X爲表示脂族烴類殘基及彼等之經取代衍生物、 氧、硫或礎醯基，Q2、X之結合位置爲相對於酚式羥基以 隣位或對位）、 1 4 _如上述9之低分子量聚苯醚，其中觸媒爲由銅化 合物、鹵素化合物及一般式（2)所示之二胺化合物所構 成、 (2)(In the formula, Qi and Q2 represent the same or different substituents, and represent hydrogen, alkyl, substituted alkyl, aralkyl, substituted aralkyl, aryl, substituted square group, alkoxy , Substituted alkoxy or halogen, and may be the same or different, respectively; X represents aliphatic hydrocarbon residues and their substituted derivatives, oxygen, sulfur or basic fluorenyl groups, and the bonding positions of Q2 and X are Ortho or para with respect to the phenolic hydroxyl group), 1 4 _ low molecular weight polyphenylene ether as described in 9 above, wherein the catalyst is composed of a copper compound, a halogen compound, and a diamine compound represented by the general formula (2) , (2)
R\ /¾ N - R5—N \ (式中，Ri、R2、R3、R4分別獨立爲氫或碳數1〜6個 之直鏈狀或分支狀烷基，且不全部同時爲氫。R5爲碳數 2〜5個之直鏈狀或具有甲基分支之伸烷基）、 15.如上述14之低分子量聚苯醚，其中觸媒爲再含 有至少一種三級單胺化合物及二級單胺化合物、 -10- (6) (6)583221 16· 一種如上述1之低分子量聚苯醚之製造方法，其 特徵爲於觸媒和s氧虱體存在下，使用低分子量聚苯醚之 良溶劑將本酣化口物予以聚合，且於聚合所得之聚苯醚溶 液中添加貧溶劑令低分子量聚苯醚析出之低分子量聚苯醚 的製造方法中，該析出爲於-80〜20 °C下進行、 17.如上述16之方法，其中貧溶劑爲碳數1〜1〇個 之醇類、 18·如上述1 6之方法，其中貧溶劑爲至少一種選自 甲醇、乙醇、丙醇、丁醇、戊醇、己醇、乙二醇、 19·如上述17或1 8之方法，其中貧溶劑爲再含有水 20- 一種如上述1之低分子量聚苯醚之製造方法，其 特徵爲於觸媒和含氧氣體之存在下令苯酚化合物聚合，且 隨著聚合之進行令低分子量聚苯醚析出之低分子量聚苯醚 之製造方法中，聚合溶劑爲二種以上之醇類的混合溶劑、 21. 如上述2〇之方法，其中聚合溶劑爲二種以上之 碳數1〜1 0個之醇類的混合溶劑、 22. 如上述 1 6之方法，其中聚合溶劑爲由甲醇、乙 醇、丙醇、丁醇、戊醇、己醇、乙二醇中選出二種以上之 醇類的混合溶劑、 23. 如上述16或20之方法，其爲包含將含有析出之 低分子量聚苯醚的流漿經由洗淨予以精製的步驟，且洗淨 溶劑爲至少一種選自甲醇、乙醇、丙醇、丁醇、戊醇、己 醇及乙二醇、 -11 - (7) (7)583221 24. 如上述23之方法，其中洗淨溶劑爲再含有水、 25. 如上述23之方法，其爲將洗淨後之低分子量聚 苯醚予以乾燥或直接脫氣除去所含有之溶劑、及 26. 如上述16或20之方法，其爲由含有析出之低分 子量聚苯醚之流漿中將低分子量聚苯醚予以分離，取得濕 潤之低分子量聚苯醚，並將其予以乾燥或直接脫氣除去所 含有之溶劑。 <用以實施發明之最佳形態> 本發明中之低分子量聚苯醚爲於30°C中於濃度0.5 g / dl之氯仿溶液中測定之還原粘度（β sp/ c )爲0.04〜 0.18 dl/g、分子量分佈（Mw/Mn)爲1.5〜2.5的低分子 量聚苯醚。 還原粘度爲使用聚苯醚作成0.5 g/dl濃度之氯仿溶 液，並將此溶液使用鳥伯類德粘度管於3(TC中進行測定 。本發明之低分子量聚苯醚的還原粘度爲0.04〜0.18 dl/ g，較佳爲 0.04 〜0.15 dl/g，更佳爲 〇·〇5 〜0.13 dl/g。 分子量分佈爲使用凝膠滲透層析（GPC )進行測定。 爲了檢量分子量則以使用標準聚苯乙烯爲佳。又，亦可使 用組合GPC和光散亂法的GPC — LALLS等。本發明之低 分子量聚苯醚的分子量分佈（Mw/Mn)爲1.5〜2.5，較 佳爲1.6〜2.4。分子量分佈爲本案發明範圍之低分子量聚 苯醚爲具有相同程度的還原粘度，且比分子量分佈爲本案 發明範圍外之低分子量聚苯醚於耐熱性和電氣特性優良。 -12- 583221 本發明之低分子量聚苯醚爲具有優良的耐熱性。使用 玻璃態化溫度（Tg )做爲表示聚苯醚之耐熱性的指標。本 發明之低分子量聚苯醚爲具有下列關係式所示之玻璃態化 溫度爲佳。R \ / ¾ N-R5—N \ (where Ri, R2, R3, and R4 are each independently hydrogen or a linear or branched alkyl group having 1 to 6 carbon atoms, and not all of them are hydrogen at the same time. R5 It is a linear or linear alkyl group having 2 to 5 carbon atoms), 15. The low molecular weight polyphenylene ether according to the above 14, wherein the catalyst further contains at least one tertiary monoamine compound and secondary Monoamine compound, -10- (6) (6) 583221 16. A method for producing a low molecular weight polyphenylene ether as described in 1 above, which is characterized by using a low molecular weight polyphenylene ether in the presence of a catalyst and a spore body. A good solvent is a method for producing a low molecular weight polyphenylene ether that polymerizes the present compound and adds a lean solvent to the polyphenylene ether solution obtained by the polymerization to precipitate a low molecular weight polyphenylene ether. The precipitation is -80 to Performed at 20 ° C, 17. The method according to the above 16, wherein the lean solvent is an alcohol having 1 to 10 carbons, 18. The method according to the above 16, wherein the lean solvent is at least one selected from the group consisting of methanol, ethanol, Propanol, butanol, pentanol, hexanol, ethylene glycol, 19. The method as described in 17 or 18 above, wherein the lean solvent is further containing water 20-one such as The method for producing a low-molecular-weight polyphenylene ether according to claim 1, which is characterized in that the phenol compound is polymerized in the presence of a catalyst and an oxygen-containing gas, and the low-molecular-weight polyphenylene ether is precipitated as the polymerization proceeds. In the method, the polymerization solvent is a mixed solvent of two or more alcohols, 21. The method as in the above 20, wherein the polymerization solvent is a mixed solvent of two or more alcohols having 1 to 10 carbons, 22. The method of 16 above, wherein the polymerization solvent is a mixed solvent of two or more alcohols selected from the group consisting of methanol, ethanol, propanol, butanol, pentanol, hexanol, and ethylene glycol. 23. As described in 16 or 20 above. A method comprising the step of purifying a slurry containing a precipitated low molecular weight polyphenylene ether by washing, and the washing solvent is at least one selected from the group consisting of methanol, ethanol, propanol, butanol, pentanol, hexanol, and Ethylene glycol, -11-(7) (7) 583221 24. The method according to the above 23, wherein the cleaning solvent contains water, 25. The method according to the above 23, which is a low molecular weight polybenzene after washing The ether is dried or directly degassed to remove the solvent, 26. The method of the above 16 or 20, which is to separate the low molecular weight polyphenylene ether from the slurry containing the precipitated low molecular weight polyphenylene ether, to obtain a wet low molecular weight polyphenylene ether, and to dry or directly Degassing removes the contained solvent. < The best form for carrying out the invention > The low molecular weight polyphenylene ether in the present invention is a reduced viscosity (β sp / c) measured at 30 ° C in a chloroform solution having a concentration of 0.5 g / dl at 0.04 ~ Low molecular weight polyphenylene ether of 0.18 dl / g and molecular weight distribution (Mw / Mn) of 1.5 to 2.5. The reduced viscosity is a chloroform solution with a concentration of 0.5 g / dl using polyphenylene ether, and this solution is measured in a 3 (TC) using a bird-type viscosity tube. The reduced viscosity of the low molecular weight polyphenylene ether of the present invention is 0.04 ~ 0.18 dl / g, preferably 0.04 to 0.15 dl / g, and more preferably 0.05 to 0.13 dl / g. The molecular weight distribution is measured using gel permeation chromatography (GPC). To check the molecular weight, use Standard polystyrene is preferred. In addition, a combination of GPC and light scattering method GPC-LALLS can be used. The molecular weight distribution (Mw / Mn) of the low molecular weight polyphenylene ether of the present invention is 1.5 to 2.5, preferably 1.6 to 2.4. The low molecular weight polyphenylene ether having a molecular weight distribution within the scope of the present invention has the same degree of reduced viscosity, and the specific molecular weight distribution of the low molecular weight polyphenylene ether outside the scope of the present invention is excellent in heat resistance and electrical characteristics. -12-583221 The low molecular weight polyphenylene ether of the invention has excellent heat resistance. The glass transition temperature (Tg) is used as an index indicating the heat resistance of the polyphenylene ether. The low molecular weight polyphenylene ether of the present invention has the following relational formula: Glassy Preferred temperature.
Tg ( C ) > 600 X [ η sp/c] + 105 式中’ T g爲以攝氏表示之低分子量聚苯醚的玻璃態化溫 度’ 〔^? sp / c〕爲表示於30°C中以0.5 g/ dl濃度之氯仿 溶液所測定之低分子量聚苯醚的還原粘度（單位：dl / g )。 本發明之低分子量聚苯醚由對於溶劑之溶解性等方面 而言’以粉末狀爲佳。本發明之低分子量聚苯醚粉末的平 均粒徑爲5.0〜1,000 //m，較佳爲5.0〜500 //m，更佳 爲5.0〜300 /zm，最佳爲5.0〜100 //m。更且，以實質 上不含有1，000 /zm以上粒子之粉末爲佳。 本發明之低分子量聚苯醚可令苯酚化合物於觸媒與含 氧氣體之存在下聚合而取得。 本發明所用之苯酚化合物爲具有如下列一般式（3 ) 構造之化合物。Tg (C) > 600 X [η sp / c] + 105 where 'T g is the glass transition temperature of low molecular weight polyphenylene ether expressed in Celsius' [^? Sp / c] is expressed at 30 ° C Reduced viscosity of low molecular weight polyphenylene ether (unit: dl / g) as measured in a chloroform solution at a concentration of 0.5 g / dl. The low molecular weight polyphenylene ether of the present invention is preferably powdery in terms of solubility in solvents and the like. The low molecular weight polyphenylene ether powder of the present invention has an average particle diameter of 5.0 to 1,000 // m, preferably 5.0 to 500 // m, more preferably 5.0 to 300 / zm, and most preferably 5.0 to 100 // m. Furthermore, it is preferable that the powder does not substantially contain particles above 1,000 / zm. The low molecular weight polyphenylene ether of the present invention can be obtained by polymerizing a phenol compound in the presence of a catalyst and an oxygen-containing gas. The phenol compound used in the present invention is a compound having a structure as shown in the following general formula (3).
式中，R6、R7、R8分別表示獨立之取代基，R6爲烷基、 經取代院基、芳院基、經取代芳院基、芳基、經取代芳基 、院氧基、經取代院氧基、r7、r8爲與Re所定義者爲 -13- 583221 Ο) 相同基並且加上亦可爲氫、鹵素。 該化合物之例可列舉例如鄰-甲苯酚、2，6 -二甲基 苯酚、2，3，6 —三甲基苯酚、2-乙基苯酚、2 —甲基一 6 —乙基苯酚、2，6 —二乙基苯酚、2-正丙基苯酚、2 —乙 基一 6 —正丙基苯酚、2-甲基—6-氯基苯酚、2 —甲基— 6 -溴基苯酚、2 —甲基一 6 -異丙基苯酚、2 -甲基一 6 — 正丙基苯酚、2 —乙基—6-溴基苯酚、2 —甲基—6 —正丁 基苯酚、2，6 —二一正丙基苯酚、2 —乙基一 6-氯基苯酚 、2 —甲基—6_苯基苯酚、2 —苯基苯酚、2，6-二苯基 苯酷、2，6 —雙（4 一赢苯基）苯酣、2-甲基—6 —甲苯 基苯酚、2，6 -二甲苯基苯酚等。此些化合物可分別單獨 使用，且亦可倂用二種以上。又，含有少量之間-甲苯酚 、對一甲苯酚、2，4一二甲基苯酚、2，4，6 —三甲基苯 酚等於實質上亦無妨。其中以2，6 -二甲基苯酚爲工業 上重要的。又，2，6-二甲基苯酚與 2，3，6—三甲基苯 酚之組合、或2，6-二甲基苯酚與2，6-二苯基苯酚之 組合亦爲較佳使用。 又，苯酚化合物以含有下述一般式（1)所示之二價 苯酚化合物爲佳。In the formula, R6, R7, and R8 each represent an independent substituent, and R6 is an alkyl group, a substituted aryl group, an aryl phenyl group, a substituted aryl phenyl group, an aryl group, a substituted aryl group, an oxy group, and a substituted aryl group Oxy, r7, and r8 are the same groups as those defined by Re (-13-583221 0), and may also be hydrogen or halogen. Examples of the compound include o-cresol, 2,6-dimethylphenol, 2,3,6-trimethylphenol, 2-ethylphenol, 2-methyl-6-ethylphenol, 2 , 6-diethylphenol, 2-n-propylphenol, 2-ethyl-6-n-propylphenol, 2-methyl-6-chlorophenol, 2-methyl-6-bromophenol, 2 -Methyl-6-isopropylphenol, 2-methyl-6-n-propylphenol, 2-ethyl-6-bromophenol, 2-methyl-6-n-butylphenol, 2,6 — Di-n-propylphenol, 2-ethyl-6-chlorophenol, 2-methyl-6-phenylphenol, 2-phenylphenol, 2,6-diphenylbenzene, 2,6-bis (4-win phenyl) phenylhydrazone, 2-methyl-6-tolylphenol, 2,6-xylylphenol, and the like. These compounds may be used singly or in combination of two or more kinds. In addition, a small amount of m-cresol, p-cresol, 2,4-dimethylphenol, and 2,4,6-trimethylphenol may be substantially equal to each other. Among them, 2,6-dimethylphenol is industrially important. A combination of 2,6-dimethylphenol and 2,3,6-trimethylphenol or a combination of 2,6-dimethylphenol and 2,6-diphenylphenol is also preferably used. The phenol compound preferably contains a divalent phenol compound represented by the following general formula (1).
OH 0HOH 0H
式中，Ql、Q2爲氫、烷基、經取代烷基、芳烷基、經取 代芳烷基、芳基、經取代芳基、烷氧基、經取代烷氧基或 -14- (10) ®素’分別可爲相同或相異亦可；X爲表示脂族烴類殘基 4彼等之經取代衍生物、氧、硫或磺醯基，q2、X之結合 iu置爲相對於酚式羥基以鄰位或對位。 該化合物之例可列舉例如下述一般式（1 一 a ) 、（ i 〜b) 、 （1— c)各個構造之化合物群。In the formula, Q1 and Q2 are hydrogen, alkyl, substituted alkyl, aralkyl, substituted aralkyl, aryl, substituted aryl, alkoxy, substituted alkoxy, or -14- (10 ) ® primes may be the same or different, respectively; X is a substituted derivative, an oxygen, a sulfur or a sulfonyl group representing an aliphatic hydrocarbon residue 4; the combination of q2 and X is relative to The phenolic hydroxyl group is ortho or para. Examples of the compound include a compound group having each structure of the following general formulae (1-a), (i ~ b), and (1-c).
(l-b)(l-b)
式中，Q1、Q 2爲氫、烷基、經取代烷基、芳烷基、經取 代芳院基、芳基、經取代芳基、烷氧基、經取代烷氧基或 It素’分別可爲相同或相異亦可；X爲脂族烴類殘基或彼 等之經取代衍生物、氧、硫或磺醯基。 具:有*i:述一般式構造之代表性物質爲Qi和q2爲甲 基且X爲異亞丙基之化合物、Ql和Q2爲甲基且χ爲伸 甲基之化合物、Qi和Q2爲甲基且X爲硫基之化合物、In the formula, Q1 and Q2 are hydrogen, alkyl, substituted alkyl, aralkyl, substituted aromatic group, aryl, substituted aryl, alkoxy, substituted alkoxy, or It's, respectively. It may be the same or different; X is an aliphatic hydrocarbon residue or their substituted derivative, oxygen, sulfur, or sulfonyl. With: * i: The representative substances of the general formula are compounds where Qi and q2 are methyl groups, and X is isopropylidene, Ql and Q2 are methyl compounds, and χ is methylene, and Qi and Q2 are Compounds in which methyl is a thio group,
QiW Q2爲甲基且X爲環亞己基之化合物等，但並非限 定於此些例。 -15- (11) (11)583221 此些二價苯酚性化合物可使用一種，且亦可組合使用 數種。二價苯酚性化合物之含量並無特別限制，但相對於 一價苯酚類，以0 . 1〜3 0莫耳％爲佳。 本發明所用之觸媒一般可使用聚苯醚製造中所用之全 部的公知觸媒系。一般已知之觸媒系爲由具有氧化還原能 力之過渡金屬離子和可與此金屬離子形成錯合之胺化合物 所構成，例如爲銅化合物和胺所構成的觸媒系、錳化合物 和胺所構成的觸媒系、鈷化合物和胺所構成的觸媒系等。 因爲聚合反應於若干之鹼性條件下可有效率進行，故此處 亦可加入若干鹼或胺。 其中，銅化合物、鹵素化合物及一般式（2)所示之 二胺化合物所構成的觸媒爲較佳使用。 R\ 严3 N - R5 - N (2) R, \ 式中，Ri、R2、R3、R4分別獨立爲氫、碳數1〜6個之 直鏈狀或分支狀烷基，且不全部同時爲氫。115爲碳數2 至5個之直鏈狀或具有甲基分支之伸烷基。 列舉此處所述之觸媒成分之銅化合物例。適當的銅化 合物可使用亞銅化合物、銅化合物或彼等之混合物。銅化 合物可例示例如氯化銅、溴化銅、硫酸銅、硝酸銅等。又 ，亞銅化合物可例示例如氯化亞銅、溴化亞銅、硫酸亞銅 、硝酸亞銅等。其中特佳之金屬化合物爲氯化亞銅、氯化 銅、溴化亞銅、溴化銅。此些銅鹽可由氧化物、碳酸鹽、 -16- (12)583221 氫氧化物等與對應之鹵素或酸於使用時合成。常用之方法 爲將氧化亞銅與鹵化氫（或鹵化氫之溶液）混合進行作成 之方法。 鹵素化合物例如爲氯化氫、溴化氫、碘化氫、氯化鈉 、溴化鈉、碘化鈉、氯化鉀、溴化鉀、碘化鉀、氯化四甲 基銨、溴化四甲基銨、碘化四甲基銨、氯化四乙基銨、溴 化四乙基銨、碘化四乙基銨等。又，彼等可以水溶液和利 用適當溶劑之溶液型式供使用。彼等鹵素化合物可單獨使 用，且亦可組合使用二種以上。較佳之鹵素化合物爲氯化 氫之水溶液、溴化氫之水溶液。 此些化合物之使用量雖無特別限定，但以銅原子相對 於苯酚化合物100莫耳以0.〇2〜0.6莫耳之範圍爲佳，且 鹵原子相對於銅原子之莫耳量以2〜2 0倍爲佳。QiW Q2 is a compound such as methyl and X is cyclohexylene, but it is not limited to these examples. -15- (11) (11) 583221 These divalent phenolic compounds may be used singly or in combination. The content of the divalent phenolic compound is not particularly limited, but it is preferably 0.1 to 30 mole% relative to the monovalent phenols. As the catalyst used in the present invention, generally all known catalyst systems used in the production of polyphenylene ether can be used. Generally known catalysts are composed of transition metal ions with redox ability and amine compounds that can form a complex with this metal ion, such as catalyst systems composed of copper compounds and amines, manganese compounds and amines. Catalyst systems, catalyst systems consisting of cobalt compounds and amines. Since the polymerization reaction can be performed efficiently under a few basic conditions, it is also possible to add a few bases or amines here. Among them, a catalyst composed of a copper compound, a halogen compound, and a diamine compound represented by the general formula (2) is preferably used. R \ Yan 3 N-R5-N (2) R, \ where Ri, R2, R3, and R4 are each independently a linear or branched alkyl group having 1 to 6 carbon atoms, and not all of them are simultaneously For hydrogen. 115 is a straight-chain or methyl-extended alkylene group having 2 to 5 carbon atoms. Examples of the copper compounds of the catalyst components described here are listed. Suitable copper compounds may be cuprous compounds, copper compounds, or mixtures thereof. Examples of the copper compound include copper chloride, copper bromide, copper sulfate, and copper nitrate. Examples of the cuprous compound include cuprous chloride, cuprous bromide, cuprous sulfate, and cuprous nitrate. Particularly preferred metal compounds are cuprous chloride, copper chloride, cuprous bromide, and copper bromide. These copper salts can be synthesized from oxides, carbonates, -16- (12) 583221 hydroxides, etc., and corresponding halogens or acids when used. A commonly used method is a method in which cuprous oxide is mixed with hydrogen halide (or a solution of hydrogen halide). The halogen compound is, for example, hydrogen chloride, hydrogen bromide, hydrogen iodide, sodium chloride, sodium bromide, sodium iodide, potassium chloride, potassium bromide, potassium iodide, tetramethylammonium chloride, tetramethylammonium bromide, Tetramethylammonium iodide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, and the like. Further, they can be used in the form of an aqueous solution and a solution using an appropriate solvent. These halogen compounds may be used alone or in combination of two or more kinds. Preferred halogen compounds are an aqueous solution of hydrogen chloride and an aqueous solution of hydrogen bromide. Although the use amount of these compounds is not particularly limited, it is preferable that the copper atom is in the range of 0.02 to 0.6 mol with respect to 100 mol of the phenol compound, and the molar amount of the halogen atom with respect to the copper atom is 2 to 20 times better.
'其次列舉觸媒成分之二胺化合物之例。可列舉例如N ，Ν，Ν’，Ν’一四甲基乙二胺、ν’ Ν，Ν·—三甲基乙二胺 、Ν，Ν’一二甲基乙二胺、Ν，Ν —二甲基乙二胺、Ν—甲 基乙二胺、Ν，Ν，Ν·，Ν，—四乙基乙二胺、Ν，Ν, Ν,— 三乙基乙二胺、Ν’ Ν’一二乙基乙二胺、ν, Ν —二乙基乙 一 fee、Ν —乙基乙一肢、N，N —二甲基—N·—乙基乙一胺 、N，N，—甲基—N —乙基乙二胺、N —正丙基乙二胺、N ，N，—正丙基乙二胺、N-異丙基乙二胺、N，N，—異丙 基乙一 0女、N —正丁基乙一胺、Ν，Ν’ —正丁基乙二胺、n —異丁基乙二胺、Ν，Ν’ —異丁基乙二胺、n—第三丁基 乙二胺、Ν，Ν·-第三丁基乙二胺、ν，ν，Ν，，Ν，一四甲 -17- (13) (13)583221 基—1，3 —二胺基丙烷、Ν，Ν，Ν· —三甲基—1，3 —二 胺基丙烷、Ν，Ν’ —二甲基—1，3 -二胺基丙烷、Ν —甲 基—1，3 —二胺基丙烷、Ν，Ν，Ν，，Ν·—四甲基—1，3 一二胺基—1—甲基丙烷、Ν，Ν，Ν·，Ν·—四甲基-1，3 —二胺基—2 —甲基丙烷、Ν，Ν，N'，F —四甲基—1，4 —二胺基丁烷、N，N，Nf，N· —四甲基_1，5 —二胺基 戊烷等。較佳之二胺化合物爲二個氮原子連接且伸烷基之 碳數爲2或3個之化合物。此些二胺化合物之使用量雖無 特別限定，但相對於苯酚化合物100莫耳以〇.〇1〜10莫 耳之範圍爲佳。 本發明中之觸媒的構成成分再含有分別單獨之三級單 胺化合物或二級單胺化合物、或其組合爲佳。 所謂三級單胺化合物爲指含有脂環式三級胺之脂族三 級胺。可列舉例如三甲胺、三乙胺、三丙胺、三丁胺、三 異丁胺、二甲基乙胺、二甲基丙胺、烯丙基二乙胺、二甲 基-正丁胺、二乙基異丙胺、N-甲基環己胺。此些三級 單胺可單獨使用，且亦可組合使用二種以上。彼等之使用 量雖無特別限定，但相對於苯酚化合物1 〇〇莫耳以1〜1 〇 莫耳之範圍爲佳。 二級單胺化合物之例於二級脂族胺可列舉例如二甲胺 、二乙胺、二正丙胺、二異丙胺、二正丁胺、二異丁胺、 二第三丁胺、二戊胺類、二己胺類、二辛胺類、二癸胺類 、二苄胺類、甲基乙胺、甲基丙胺、甲基丁胺、環己胺。 含有芳香族之二級單胺化合物之例可列舉N -苯基甲醇胺 -18- (14) (14)583221 、N —苯基乙醇胺、N —苯基丙醇胺、N—(間一甲基苯基 )乙醇胺、N- （對—甲基苯基）乙醇胺、N— ( 2·，6·— 二甲基苯基）乙醇胺、N—(對一氯苯基）乙醇胺、N — 乙基苯胺、N-丁基苯胺、N-甲基一 2 —甲基苯胺、N-甲基一 2，6 -二甲基苯胺、二苯胺等，但並非限定於此些 例。此些二級胺可單獨使用，且亦可組合使用二種以上。 使用量雖無特別限定，但相對於苯酚化合物1 00莫耳以 0.05〜15莫耳爲佳，且以〇.1〜1〇莫耳之範圍爲更佳。 將二級單胺化合物與三級單胺化合物分別做爲觸媒的 構成成分，且可分別單獨使用，並且亦可組合使用。 更且，添加已知具有提高聚合活性效果之界面活性劑 亦爲佳。例如，以Aliqu at 3 3 6和Capri qu at商品名已知的 氯化三辛基甲基銨。使用量爲相對於聚合反應混合物之全 量以不超過0 . 1 w t %之範圍爲佳。 本發明聚合中之含氧氣體除了純氧以外，可使用氧和 氮等之惰性氣體以任意比例混合之氣體、和空氣、以及空 氣與氮等之惰性氣體以任意比例混合之氣體等。聚合反應 中之系內壓力爲常壓即充分，但視需要亦可使用減壓或加 壓。 聚合溫度雖無特別限定，若過低則難進行反應，若過 高則反應的選擇性降低，故以 〇〜8〇°C，較佳爲10〜70 °C之範圍進行爲佳。 關於聚合反應終了後之後處理方法並無特別限制。通 常使用加入鹽酸和醋酸等之酸、或乙二胺四醋酸（EDT a -19- (15) )及其鹽、或三醋酸胺及其鹽等令觸媒失活之方法。 又，通常之聚苯醚聚合所副生成之已知的二苯醌等副 產物的處理方法亦無特別限制。如上述，若觸媒之金屬離 子爲以實質上失活之狀態，則僅進行加熱即可脫色。又， 將氫醌、亞連二硫酸鈉等之還原劑添加必要量之方法亦可 。此步驟之溫度雖無特別限定，但以1 0〜1 0 0 °c之溫度條 件下進行於作業上爲佳。 一般取得聚苯醚之方法已知有使用聚苯醚之貧溶劑做 爲聚合溶劑，隨著聚合之進行令聚苯醚以粒子型式析出的 沈澱聚合法、和使用良溶劑做爲聚合溶劑，且將聚苯酸於 溶劑中溶解的溶液聚合法，而本發明之低分子量聚苯旨迷以 任一種方法均可取得。 於使用聚苯醚之貧溶劑做爲聚合溶劑，隨著聚合之進 行令聚苯醚析出之沈澱聚合法之情形中，必須使用二種以 上之醇類的混合溶劑做爲貧溶劑。 貧溶劑以碳數1〜1 0個之醇類爲佳。更佳爲由甲醇、 乙醇、丙醇、丁醇、戊醇、己醇、乙二醇選出二種以上。 此貧溶劑爲不含有水爲佳。 若爲二種以上則選擇何種並無特別限制。又，混合溶 劑中之各種溶劑的比例並無特別限定，且達成本發明方法 所必要之聚合溶劑的組合和比率可由此些溶劑中選取，故 可在非常廣泛之範圍中選擇，但由工業性觀點而言，則爲 考慮價格、回收方法之難易度等，且當然加以某程度的限 制0 -20- (16) (16)583221 令人驚訝地，若使用二種以上之醇類的混合溶劑，則 儘管分別對於低分子量聚苯醚爲貧溶劑，但仍可經由改變 其比率而控制所得低分子量聚苯醚的分子量，並且顯示出 比僅使用一種醇類之單獨溶劑時更加提高聚合活性和產率 之極爲特異的舉動。 於聚合溶劑中，在不會溶解低分子量聚苯醚之範圍下 ，可令良溶劑共存亦無妨。因此，必須注意所謂完全不包 含之意義。例如，於還原粘度爲0.07 dl/ g之低分子量聚 苯醚之情形中，於甲醇與正丁醇之混合溶劑中亦可含有少 量的二甲苯（1 %左右）。聚苯醚之還原粘度若變低，則 可共存之良溶劑份量減少。於還原粘度爲0.04 dl/ g之低 分子量聚苯醚之情形中，所容許共存之二甲苯份量爲5 0 ppm左右。良溶劑之份量爲根據所欲之低分子量聚苯醚的 還原粘度、或根據良溶劑對於低分子量聚苯醚之親和性程 度而異，無法一槪而論，且當然爲根據各個溶劑種類而異 〇 另一方面，於使用聚苯醚之良溶劑做爲聚合溶劑，且 於含有所得低分子量聚苯醚之溶液中添加貧溶劑令低分子 量聚苯醚析山之溶液聚合法之情形中，該析出必須於—8 0 〜+ 2 (TC之範圍下進行。 良溶劑可列舉苯、甲苯、二甲苯（包含鄰—、間-、 對-之各異構物）、乙苯、苯乙烯等之芳香族烴類、氯仿 、二氯甲烷、1，2-二氯乙烷、氯苯、二氯苯等之鹵化烴 類、硝基苯等之硝基化合物。較佳之良溶劑爲甲苯。雖具 -21 - (17) (17)583221 有若干貧溶劑性但被分類成良溶劑之物質可例示戊烷、己 烷、庚烷、環己烷、環庚烷等之脂族烴類、醋酸乙酯、甲 酸乙酯等之酯類、四氫呋喃、二乙醚等之醚類、二甲基亞 硕等。此些良溶劑可單獨使用，且亦可組合使用二種以上 。更且，於聚合後之反應混合物爲溶液之範圍下，含有醇 類和水等之貧溶劑亦無妨。 經由聚合取得含有低分子量聚苯醚和溶劑之溶液。溶 液中之低分子量聚苯醚的濃度雖無特別限制，但以25〜 7 〇重量％爲佳。 經由對所得之溶液添加貧溶劑則可析出低分子量聚苯 醚•貧溶劑可列舉醚類、酮類或醇類。較佳爲碳數1〜i 〇 個之醇類，更佳爲由甲醇 '乙醇、丙醇、丁醇、戊醇、己 醇及乙二醇中選出至少一種。更且亦可含有水。 令低分子量聚苯醚析出之方法中，對於裝置和手段並 無特別限制。可列舉於具有攪拌機之適當大小之槽中連續 添加含有低分子量聚苯醚之溶液和貧溶劑之方法，於放入 含有低分子量聚苯醚溶液之槽中添加貧溶劑之方法，於放 入貧丨谷劑之槽中添加含有低分子量聚苯麟溶液之方法，於 管型靜態混合器中連續添加含有低分子量聚苯醚之溶液和 貧溶劑之方法等各種方法。 於析出裝置中供給之含有低分子量聚苯醚溶液之溫度 及貧溶劑之溫度雖無特別限制，但必須充分注意析出裝置 中之析出操作的溫度。爲了取得本發明之低分子量聚苯醚 ，必須於-80〜+20 °C之範圍下進行析出。若超過2〇t -22- (18) ’則低分子量聚苯醚附著至反應器等，且無法析出低分子 量聚苯醚。又，未滿- 80°C雖亦可取得低分子量聚苯醚， 但於溫度下降至未滿-80t則需要極大之能量，非爲有效 率的。 上述任一*種方法均可取得含有低分子量聚苯_和溶劑 之流漿。本發明之低分子量聚苯醚可由流漿中除去殘存之 溶劑而取得。除去溶劑之方法可列舉將流漿予以固液分離 ’取得濕潤低分子量聚苯醚，並將其乾燥或以直接脫氣法 取得低分子量聚苯醚之方法。 固液分離之手段並無特別限制。可使用先前已知之全 部方法。例如過濾型離心分離器、附有刮搔槳葉之離心分 離器、真空鼓型過濾器、努采漏斗等之物質均可使用。還 有，使用良溶劑做爲聚合溶劑，且於低溫下析出取得之流 獎時，必須令最初的過濾溫度以析出溫度所述之溫度範圍 下進行。 於乾燥或直接脫氣法之前，所得之濕潤低分子量聚苯 醚以該低分子量聚苯醚之貧溶劑予以洗淨爲佳。洗淨溶劑 由甲醇、乙醇、丙醇、丁醇、戊醇、己醇及乙二醇選出至 少一種爲佳。令洗淨溶劑中再含有水之方法爲較佳態樣。 令所得之濕潤低分子量聚苯醚以乾燥或直接脫氣法， 則可取得低分子量聚苯醚。關於乾燥方法並無特別限制。 可使用先前已知的全部方法。例如，漿葉乾燥器、真空乾 燥機、噴霧乾燥器、加熱管乾燥器等均可使用。特別於惰 性氣體下之操作爲佳。此類乾燥方法下，本發明之低分子 -23- (19) 量聚苯醚爲以粉體型式取得。直接脫氣方法爲將所得之濕 潤聚苯醚加熱除去揮發性溶劑等之方法。此方法可列舉例 如將濕潤低分子量聚苯醚供給至經加熱的脫氣擠壓機，一 邊令揮發性成分脫氣一邊將型板所排出之本發明之低分子 量聚苯醚予以冷却切斷，取得九狀物之方法，將放入濕潤 低分子量聚苯醚之適當容器予以加熱減壓，一邊除去溶劑 一邊令本發明之低分子量聚苯醚凝固，其次，由容器中強 制排出之方法等。亦可採用例示以外之任何方法。直接脫 氣法中，所得之聚苯醚爲包含九狀物和大塊狀物。於本發 明中，將此形態之物質再以粉碎等之方法作成粉體爲佳。 本發明之低分子量聚苯醚爲具有優良的耐熱性及電氣 特性，且極有用於要求低介電率和低介電損失等之電子材 料用途。又，因爲本發明之低分子量聚苯醚粉末爲粒徑小 ，故例如使用於預浸漬物之製造過程等，於其後之製造步 驟等使用時之對於溶劑的溶解性爲極迅速，且與各種變性 反應試藥的反應性優良，由提高電子材料生產性之觀點而 言爲較佳使用。 更佳’本發明之低分子量聚苯醚亦可應用於各種熱可 塑性樹脂組成物和熱硬化性樹脂等。本發明之低分子量聚 苯醚具有令各種熱可塑性樹脂組成物可塑化之效果，且做 爲可塑劑之應用亦良好。當然於使用通常高分子量之聚苯 醚之改質聚苯醚樹脂中，應用本發明之低分子量聚苯醚， 亦有助於改善其流動特性。 熱可塑性樹脂例如爲聚苯乙烯系樹脂（亦包含橡膠增 -24- (20) (20)583221 強之聚苯乙烯和AS、ABS樹脂等）、聚醯胺樹脂、聚烯 烴系樹脂、聚酯樹脂、液晶樹脂、熱可塑性彈性體等之組 成物、熱硬化性樹脂可列舉例如環氧系、不飽和聚酯系、 聚胺基甲酸乙酯、交聯芳基、雙馬來醯亞胺、酚性樹脂等 Z組成物’但並非限定於此例。特別，因爲本發明之低分 _ 子量聚苯醚具有本來聚苯醚所擁有的難燃性，故可用於做 爲對其他耐熱、難燃性差之物質賦與耐熱性、難燃性之耐 熱、難燃助劑性之添加劑。特別，極有用於聚苯乙烯和熱 · 可塑性彈性體的改質。 又’製造含有本發明之低分子量聚苯醚之樹脂組成物 時，可添加其他添加劑，例如可塑劑、安定劑、改質劑、 紫外線吸收劑、難燃劑、著色劑、脫模劑及玻璃纖維、碳 纖維等之纖維狀增強劑、及玻璃珠粒、碳酸鈣、滑石等之 充塡劑。安定劑和改質劑可列舉亞磷酸酯類、受阻酚類、 含硫抗氧化劑、烷醇胺類、醯胺類、二硫基胺甲酸金屬鹽 類、無機硫化物、金屬氧化物類、羧酸酐類、苯乙烯和丙 w 烯酸硬脂酯等之二烯親和物類、含環氧基之化合物等，但 並非限定於此例。此些添加劑可單獨或組合使用。 將構成含有本發明之低分子量聚苯醚之樹脂組成物的 各成分予以混合之方法可爲任一種方法，例如，可使用溶 — 液摻混合脫氣方法、擠壓機、加熱輥、班伯利混合器、揑 - 和器、H e n s h e 11混合器等。 【實施方式】 -25- (22) (22)583221 之重量平均分子量（Mw)與數平均分子量（Μη)之比之 分子量分佈（Mw/Mn)。 (4 )聚苯醚粒徑 將各例所得之聚苯醚以開孔1，000从m之篩過篩， 並且對篩上殘留之聚苯醚量進行重量測定。其次將通過篩 之聚苯醚，使用雷射粒度分析計SALD — 2000 (島津製作 所（株）製）並且分散於甲醇中，進行粒徑測定。篩上殘 留之聚苯醚超過過篩聚苯醚全量之50 wt%時，粒徑視爲 > 1,000 // m 0 (5 )聚苯醚之玻璃態化溫度（Tg) 玻璃態化溫度（Tg )之測定爲使用PERKIN ELMAR ( 株）製 DSC ( Differential Scanning Calorimeter，差示掃描 熱量計）商品名Pyris卜於氮氛圍氣下，以升溫速度20°C / min由5 0°C至300 °C爲止進行2回掃描。由第二回掃描 所得之比熱曲線求出Tg。 (6 )聚苯醚之比介電率 將測定對象之聚苯醚使用150 mmx 150 mmX 2 mm之 金屬模具，以（株）神藤金屬工業所製加壓成型機（ TEST PRESS YSR — 10型）進行加壓成形。使用所得加壓 片之一部分，根據HS — K 6911規格試驗法，測定1 MHz 中之比介電率。測定裝置爲使用 Hewlett Packard公司的 -27- (23) (23)583221'Next is an example of a diamine compound as a catalyst component. Examples include N, N, N ', N'-tetramethylethylenediamine, ν'N, N · -trimethylethylenediamine, N, N'-dimethylethylenediamine, N, N- Dimethylethylenediamine, N-methylethylenediamine, Ν, Ν, Ν ·, Ν, -tetraethylethylenediamine, Ν, Ν, Ν, -triethylethylenediamine, Ν 'Ν' Monodiethylethylenediamine, ν, Ν-diethylethylene-fee, Ν-ethylethanelimb, N, N-dimethyl-N · -ethylethyleneamine, N, N, -methyl-N —Ethylethylenediamine, N —n-propylethylenediamine, N, N, —n-propylethylenediamine, N-isopropylethylenediamine, N, N, —isopropylethylene-10, N —N-butylethylenediamine, N, N ′ —n-butylethylenediamine, n —isobutylethylenediamine, N, N ′ —isobutylethylenediamine, n—thirdbutylethylenediamine, Ν, Ν · -tert-butylethylenediamine, ν, ν, Ν, Ν, tetramethyl-17- (13) (13) 583221 group-1,3-diaminopropane, Ν, Ν, Ν · —trimethyl-1,3-diaminopropane, Ν, Ν′-dimethyl-1,3-diaminopropane, Ν—methyl-1,3-diaminopropane, Ν Ν, Ν ,, Ν · —tetramethyl-1,3-diamino-1-methylpropane, Ν, Ν, Ν ·, Ν · —tetramethyl-1,3-diamino-2— Methylpropane, N, N, N ', F -tetramethyl-1,4-diaminobutane, N, N, Nf, N · -tetramethyl_1,5-diaminopentane, etc. . Preferred diamine compounds are compounds in which two nitrogen atoms are connected and the number of carbons of the alkylene group is 2 or 3. Although the amount of these diamine compounds to be used is not particularly limited, it is preferably in the range of 0.01 to 10 mols relative to 100 mols of the phenol compound. It is preferable that the constituent components of the catalyst in the present invention further contain a separate tertiary monoamine compound or a secondary monoamine compound, or a combination thereof. The tertiary monoamine compound refers to an aliphatic tertiary amine containing an alicyclic tertiary amine. Examples include trimethylamine, triethylamine, tripropylamine, tributylamine, triisobutylamine, dimethylethylamine, dimethylpropylamine, allyldiethylamine, dimethyl-n-butylamine, and diethylamine. Isopropylamine, N-methylcyclohexylamine. These tertiary monoamines may be used alone or in combination of two or more kinds. Although the amounts of these are not particularly limited, it is preferably in the range of 1 to 100 mol relative to 1,000 mol of the phenol compound. Examples of the secondary monoamine compound include secondary amines such as dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-tert-butylamine, and dipentyl. Amine, dihexylamine, dioctylamine, didecylamine, dibenzylamine, methylethylamine, methylpropylamine, methylbutylamine, cyclohexylamine. Examples of the aromatic-containing secondary monoamine compound include N-phenylmethanolamine-18- (14) (14) 583221, N-phenylethanolamine, N-phenylpropanolamine, N- (m-A Phenyl) ethanolamine, N- (p-methylphenyl) ethanolamine, N- (2 ·, 6 · -dimethylphenyl) ethanolamine, N- (p-chlorophenyl) ethanolamine, N-ethyl Aniline, N-butylaniline, N-methyl-1 -methylaniline, N-methyl-2,6-dimethylaniline, diphenylamine, etc. are not limited to these examples. These secondary amines can be used alone or in combination of two or more. Although the amount to be used is not particularly limited, it is preferably from 0.05 to 15 mol, and more preferably from 0.1 to 10 mol relative to 100 mol of the phenol compound. The secondary monoamine compound and the tertiary monoamine compound are respectively used as constituents of the catalyst, and they can be used separately or in combination. Furthermore, it is also preferable to add a surfactant which is known to have an effect of increasing polymerization activity. For example, trioctylmethylammonium chloride is known under the trade names Aliqu at 3 36 and Capri qu at. The amount used is preferably within a range of not more than 0.1 wt% relative to the total amount of the polymerization reaction mixture. In addition to pure oxygen, the oxygen-containing gas in the polymerization of the present invention may be a gas mixed with an inert gas such as oxygen and nitrogen at an arbitrary ratio, and air, and a gas mixed with an inert gas such as air and nitrogen at an arbitrary ratio. The internal pressure in the polymerization reaction is sufficient if it is normal pressure, but if necessary, reduced pressure or pressure may be used. Although the polymerization temperature is not particularly limited, if it is too low, the reaction is difficult to proceed, and if it is too high, the selectivity of the reaction is reduced. Therefore, it is preferably carried out in the range of 0 to 80 ° C, preferably 10 to 70 ° C. There is no particular limitation on the processing method after the polymerization reaction is completed. The catalyst is usually inactivated by adding acids such as hydrochloric acid and acetic acid, or ethylenediaminetetraacetic acid (EDT a -19- (15)) and its salts, or amine triacetate and its salts. There is also no particular limitation on the method of treating known by-products such as dibenzoquinone, which are by-produced by the polymerization of polyphenylene ether. As described above, if the metal ions of the catalyst are in a substantially deactivated state, they can be decolored by simply heating. Also, a method of adding a necessary amount of a reducing agent such as hydroquinone, sodium bisthionite, or the like may be used. Although the temperature of this step is not particularly limited, it is preferable to perform the operation at a temperature of 10 to 100 ° C. Generally, methods for obtaining polyphenylene ether are known to use a lean solvent of polyphenylene ether as a polymerization solvent, a precipitation polymerization method in which polyphenylene ether is precipitated in a particle form as the polymerization progresses, and a good solvent is used as the polymerization solvent, and A solution polymerization method in which polyphenylic acid is dissolved in a solvent, and the low molecular weight polybenzene of the present invention can be obtained by any method. In the case of using a poor solvent of polyphenylene ether as a polymerization solvent and a precipitation polymerization method in which polyphenylene ether is precipitated along with the polymerization, a mixed solvent of two or more alcohols must be used as the lean solvent. The lean solvent is preferably an alcohol having 1 to 10 carbon atoms. More preferably, two or more kinds are selected from methanol, ethanol, propanol, butanol, pentanol, hexanol, and ethylene glycol. The lean solvent is preferably free of water. If there are two or more types, there is no particular limitation on which one is selected. In addition, the ratio of various solvents in the mixed solvent is not particularly limited, and the combination and ratio of polymerization solvents necessary to achieve the method of the present invention can be selected from these solvents, so it can be selected from a very wide range, but it is industrial From the standpoint of consideration, it is to consider the price, the ease of recovery methods, etc., and of course, to some extent. 0 -20- (16) (16) 583221 Surprisingly, if a mixed solvent of two or more alcohols is used , Although the low-molecular-weight polyphenylene ether is a poor solvent, the molecular weight of the obtained low-molecular-weight polyphenylene ether can be controlled by changing its ratio, and it shows that the polymerization activity and A very specific act of yield. In the polymerization solvent, a good solvent can coexist in a range where the low molecular weight polyphenylene ether will not be dissolved. Therefore, it is necessary to pay attention to the meaning of the so-called total exclusion. For example, in the case of reducing a low molecular weight polyphenylene ether having a viscosity of 0.07 dl / g, a small amount of xylene (about 1%) may be contained in a mixed solvent of methanol and n-butanol. If the reduced viscosity of the polyphenylene ether becomes low, the amount of good solvent that can coexist decreases. In the case of reducing a low molecular weight polyphenylene ether having a viscosity of 0.04 dl / g, the allowable amount of co-existing xylene is about 50 ppm. The amount of good solvent varies according to the desired reduced viscosity of the low molecular weight polyphenylene ether, or according to the degree of affinity of the good solvent for the low molecular weight polyphenylene ether, which cannot be said at one glance, and of course varies according to the type of each solvent 〇 On the other hand, in the case of a solution polymerization method using a good solvent of polyphenylene ether as a polymerization solvent, and adding a lean solvent to a solution containing the obtained low molecular weight polyphenylene ether to make low molecular weight polyphenylene ether Precipitation must be performed in the range of -8 0 to + 2 (TC. Good solvents include benzene, toluene, xylene (including the isomers of o-, m-, and p-), ethylbenzene, styrene, etc. Aromatic hydrocarbons, chloroform, dichloromethane, 1,2-dichloroethane, halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, and nitro compounds such as nitrobenzene. The preferred good solvent is toluene. -21-(17) (17) 583221 Some substances which are poor in solvent but classified as good solvents can be exemplified by aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, cycloheptane, ethyl acetate, etc. , Esters such as ethyl formate, ethers such as tetrahydrofuran, diethyl ether, etc. Methylasco, etc. These good solvents can be used alone or in combination of two or more. Moreover, as long as the reaction mixture after polymerization is a solution, a poor solvent containing alcohols, water, etc. may be used. A solution containing low-molecular-weight polyphenylene ether and a solvent is obtained through polymerization. Although the concentration of the low-molecular-weight polyphenylene ether in the solution is not particularly limited, it is preferably 25 to 70% by weight. By adding a poor solvent to the obtained solution, Examples of the precipitated low molecular weight polyphenylene ether • Lean solvents include ethers, ketones or alcohols. Alcohols having 1 to 100 carbon atoms are preferred, and methanol, ethanol, propanol, butanol, and pentanol are more preferred. At least one selected from the group consisting of hexanol and ethylene glycol. It may also contain water. In the method for precipitating low molecular weight polyphenylene ether, there are no particular restrictions on the device and means. It can be listed in a tank of a suitable size with a mixer Method for continuously adding a solution containing a low molecular weight polyphenylene ether and a lean solvent, adding a lean solvent to a tank containing a low molecular weight polyphenylene ether solution, and adding a low molecular weight to a tank containing a lean cereal Various methods such as a method of benzin solution, a method of continuously adding a solution containing a low molecular weight polyphenylene ether and a lean solvent in a tube-type static mixer, and a temperature and a lean solvent containing a low molecular weight polyphenylene ether solution supplied in a precipitation device. Although the temperature is not particularly limited, full attention must be paid to the temperature of the precipitation operation in the precipitation device. In order to obtain the low molecular weight polyphenylene ether of the present invention, the precipitation must be performed within a range of -80 to +20 ° C. If it exceeds 2 ° t -22- (18) 'The low molecular weight polyphenylene ether is attached to the reactor, etc., and the low molecular weight polyphenylene ether cannot be precipitated. Moreover, although low molecular weight polyphenylene ether can be obtained at temperatures below -80 ° C, Lowering to less than -80t requires great energy and is not efficient. Any of the above * methods can obtain a slurry containing low molecular weight polyphenylene and a solvent. The low molecular weight polyphenylene ether of the present invention can be obtained from a slurry Obtained by removing the remaining solvent. The method of removing the solvent includes a method of solid-liquid separation of the slurry, to obtain a wet low-molecular-weight polyphenylene ether, and drying or obtaining a low-molecular-weight polyphenylene ether by direct degassing. The means of solid-liquid separation is not particularly limited. All previously known methods can be used. For example, a filter type centrifugal separator, a centrifugal separator with a scraper blade, a vacuum drum filter, a hopper, etc. can be used. In addition, when a good solvent is used as a polymerization solvent, and the obtained stream is precipitated at a low temperature, the initial filtration temperature must be performed within the temperature range described in the precipitation temperature. Prior to the drying or direct degassing method, the obtained wet low molecular weight polyphenylene ether is preferably washed with a lean solvent of the low molecular weight polyphenylene ether. The washing solvent is preferably at least one selected from methanol, ethanol, propanol, butanol, pentanol, hexanol and ethylene glycol. The method of making water in the washing solvent is preferable. Low-molecular-weight polyphenylene ether can be obtained by drying or directly degassing the obtained wet low-molecular-weight polyphenylene ether. There is no particular limitation on the drying method. All previously known methods can be used. For example, a paddle dryer, a vacuum dryer, a spray dryer, a heating tube dryer, and the like can be used. Especially for inert gas operation. Under this type of drying method, the low molecular weight -23- (19) polyphenylene ether of the present invention is obtained as a powder. The direct degassing method is a method in which the obtained wet polyphenylene ether is heated to remove volatile solvents and the like. This method includes, for example, supplying a wet low-molecular-weight polyphenylene ether to a heated degassing extruder, and cooling and cutting off the low-molecular-weight polyphenylene ether of the present invention discharged from a mold while degassing volatile components. The method of obtaining nine objects is to put a suitable container of wet low molecular weight polyphenylene ether under reduced pressure, remove the solvent, and solidify the low molecular weight polyphenylene ether of the present invention. Second, a method of forcibly discharging from the container. Any method other than the example may be used. In the direct degassing method, the obtained polyphenylene ether contains nine substances and large blocks. In the present invention, it is preferable that the substance in this form is powdered by a method such as pulverization. The low-molecular-weight polyphenylene ether of the present invention has excellent heat resistance and electrical characteristics, and is extremely useful for electronic materials requiring low dielectric constant, low dielectric loss, and the like. In addition, since the low molecular weight polyphenylene ether powder of the present invention has a small particle size, it is used, for example, in the manufacturing process of prepregs, etc., and its solubility in solvents when used in subsequent manufacturing steps is extremely rapid, and Various denaturation reaction reagents are excellent in reactivity and are preferably used from the viewpoint of improving the productivity of electronic materials. More preferably, the low molecular weight polyphenylene ether of the present invention can also be applied to various thermoplastic resin compositions, thermosetting resins, and the like. The low-molecular-weight polyphenylene ether of the present invention has the effect of plasticizing various thermoplastic resin compositions, and has good application as a plasticizer. Of course, in a modified polyphenylene ether resin using a generally high molecular weight polyphenylene ether, the application of the low molecular weight polyphenylene ether of the present invention can also help improve its flow characteristics. The thermoplastic resin is, for example, a polystyrene resin (including rubber-enhanced polystyrene and AS, ABS resin, etc.), polyamide resin, polyolefin resin, and polyester. Examples of the composition of the resin, liquid crystal resin, thermoplastic elastomer, and thermosetting resin include epoxy-based, unsaturated polyester-based, polyurethane, cross-linked aryl, bismaleimide, The Z composition such as a phenol resin is not limited to this example. In particular, since the low-molecular-weight polyphenylene ether of the present invention has the flame retardance originally possessed by polyphenylene ether, it can be used as heat resistance for imparting heat resistance and flame retardancy to other materials with poor heat resistance and flame retardance Flame retardant additives. In particular, it is extremely useful for the modification of polystyrene and thermoplastic elastomers. In addition, when manufacturing a resin composition containing the low molecular weight polyphenylene ether of the present invention, other additives such as plasticizers, stabilizers, modifiers, ultraviolet absorbers, flame retardants, colorants, release agents, and glass may be added. Fibrous reinforcing agents such as fibers and carbon fibers, and fillers such as glass beads, calcium carbonate, and talc. Examples of stabilizers and modifiers include phosphites, hindered phenols, sulfur-containing antioxidants, alkanolamines, amidoamines, metal dithiocarbamates, inorganic sulfides, metal oxides, and carboxylic acids. Acid anhydrides, diene affinity materials such as styrene and stearyl acrylate, epoxy-containing compounds, and the like are not limited to this example. These additives can be used alone or in combination. The method of mixing the components constituting the resin composition containing the low-molecular-weight polyphenylene ether of the present invention may be any method. For example, a solution-liquid mixing and degassing method, an extruder, a heating roller, and a Banbury may be used. Lee mixer, pinch-and-mixer, Henshe 11 mixer, etc. [Embodiment] The molecular weight distribution (Mw / Mn) of the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mη) of -25- (22) (22) 583221. (4) Particle size of polyphenylene ether The polyphenylene ether obtained in each example was sieved through a sieve with an opening of 1,000 m, and the amount of polyphenylene ether remaining on the sieve was measured by weight. Next, the polyphenylene ether that passed the sieve was dispersed in methanol using a laser particle size analyzer SALD-2000 (manufactured by Shimadzu Corporation), and the particle size was measured. When the residual polyphenylene ether on the sieve exceeds 50 wt% of the total amount of sieved polyphenylene ether, the particle size is regarded as > 1,000 // m 0 (5) Glass transition temperature (Tg) of glass transition temperature ( Tg) was measured using DSC (Differential Scanning Calorimeter) manufactured by PERKIN ELMAR Co., Ltd. under the trade name Pyris. Under a nitrogen atmosphere, the temperature was increased from 20 ° C / min to 50 ° C to 300 °. Scan up to 2 times. Tg was obtained from the specific heat curve obtained from the second scan. (6) Specific permittivity of polyphenylene ether The polyphenylene ether to be measured is a 150 mm x 150 mm x 2 mm metal mold, and a press molding machine (TEST PRESS YSR — 10) manufactured by Kondo Metal Industry Co., Ltd. Press forming. Using a part of the obtained pressed sheet, the specific permittivity in 1 MHz was measured according to the HS-K 6911 specification test method. The measuring device was Hewlett Packard's -27- (23) (23) 583221
Presion LCR Meter CHP— 4284A 型）。 實施例1 於反應器底部具備用以導入含氧氣體的噴霧器、攪拌 渦輪翼及擋板、反應器上方之通風氣體流線中具備迴流冷 却器之1.5公升附有套管之反應器中，放入0.2512克之氯 化銅二水合物、1.1 062克之35%鹽酸、3.6179克之二正 丁胺、9.5937克之 Ν，Ν，Ν，，Ν’ —四甲基丙烷二胺、 211.63克之甲醇及493.80克之正丁醇及180.0克之2，6 -二甲基苯酚。溶劑之組成重量比爲正丁醇：甲醇=70 : 30。其次一邊激烈攪拌一邊對反應器以180 ml / min之速 度由噴霧器開始導入氧，且同時於套管中通入熱媒將聚合 溫度調節保持於40°C。聚合液立即呈現流漿之態樣。聚 合中，未觀測到附著至反應器。開始導入氧氣1 20分鐘後 ，停止氧的通氣，並於所得之聚合混合物中添加乙二胺四 醋酸三鉀鹽（同仁化學硏究所製試藥）之1 〇 %水溶液， 且保溫於5 0 °C。其次將氫醌（和光純藥公司製試藥）各 少量添加，且持續於5 0 °C保溫直到流漿狀之聚苯醚變成 白色爲止。終了後，過濾，並將濾渣之濕潤聚苯醚投入含 有5 0 %水之甲醇洗淨溶劑，且於60 °C進行攪拌。繼續再 過濾，於濾渣上撒以含有50 %水之甲醇予以洗淨’取得 濕潤聚苯醚。其次於11 0 °C真空乾燥取得乾燥之聚苯醚。 平均粒徑爲56 Mm、l，〇〇〇 /zm以上之粒子並不存在。 又，進行Wsp / c、產率、分子量分佈、Tg及比介電率之 -28- (24) (24)583221 測定。結果示於表1。 實施例2 除了未改變所使用溶劑之全量且令組成重量比爲正丁 醇：甲醇=30 : 70以外，以實施例1之方法進行。聚合 中，未觀測到附著至反應器。所得之聚苯醚之平均粒徑爲 34 β m ' 1,000 // m以上之粒子並未存在。又，同實施例 1進行各測定且結果示於表1。 實施例3 除了未改變所使用溶劑之全量且令組成重量比爲正丁 醇：甲醇=1 〇 : 90以外，以實施例1之方法進行。聚合 中，未觀測到附著至反應器。所得之聚苯醚之平均粒徑爲 39 β m ^ 1,000 // m以上之粒子並未存在。又，同實施例 1進行各測定且結果示於表1。 比較例1 除了未改變所使用溶劑之全量且令組成重量比爲正丁 醇：甲醇=〇 : 1 〇〇，即除了以甲醇單獨溶劑，聚合時間爲 240分鐘以外，以實施例1之方法進行。聚合中，未觀測 到附著至反應器。所得之聚苯醚之平均粒徑爲15 // m、 1,000 // m以上之粒子並未存在。又，同實施例1進行各 測定且結果示於表1。 -29- (25) (25)583221 比較例2 除了單獨使用經水飽和之正丁醇做爲溶劑，聚合時間 爲240分鐘以外，以實施例1之方法進行。聚合中，未觀 測到附著至反應器。所得之聚苯醚之平均粒徑爲3 9 // m . ' 1,000 // m以上之粒子並未存在。又，同實施例1進行 各測定且結果示於表1。 比較例3 ♦ 除了未改變所使用溶劑之全量且令組成重量比爲二甲 苯：正丁醇：甲醇=60 : 20 : 20，使用甲醇做爲洗淨溶劑 以外，以實施例1之方法進行。聚合中觀測到多量附著至 反應器。所得之聚苯醚之平均粒徑爲920 // m、1，000 # m以上之粒子爲存在46 %。同實施例1進行各測定且結 果示於表1。 比較例4 除了令聚合時間爲5 5分鐘以外，以比較例3之方法 進行。聚合中觀測到多量附著至反應器。所得之聚苯醚之 平均粒徑爲850 /zm、1,〇〇〇 //m以上之粒子爲存在38% 。又，同實施例1進行各測定且結果示於表1。 實施例4 除了使用2，6 —二甲基苯酚126克、和2，3，6 —三 甲基苯酚5 4克做爲苯酚化合物以外，以實施例2同樣之 -30- (26) (26)583221 方法進行。聚合中未觀測到附著至反應器。所得之聚苯醚 之平均粒徑爲43 # m、l，〇〇〇 /zm以上之粒子並未存在 。又，同實施例1進行各測定且結果示於表1。 實施例5 除了使用2，6 —二甲基苯酚126克、和2，6 —二苯 基酚54克做爲酚性化合物，做爲觸媒成分二胺之〇.169〇 克N，N，N’，N’ —四甲基乙二胺，聚合溫度爲60°C，聚 合時間爲1 80分鐘以外，以實施例2同樣之方法進行。聚 合中未觀測到附著至反應器。所得之聚苯醚之平均粒徑爲 33 β m ' 1,000 以上之粒子並未存在。又，同實施例 1進行各測定且結果示於表1。 實施例6 除了未改變所使用溶劑之全量且令組成重量比爲正己 醇：甲醇=10 : 90，使用甲醇：水=90 : 10重量比所構成 之溶劑做爲洗淨溶劑以外，以實施例1之方法進行。聚合 中，未觀測到附著至反應器。所得之聚苯醚之平均粒徑爲 54 // m ' 1,000 //m以上之粒子並未存在。同實施例1進 行各測定且結果示於表1。 實施例7 除了苯酚化合物爲使用2.5莫耳％之含有2，2—雙（ 3，5 —二甲基一 4一羥苯基）丙烷的2，6-二甲基苯酚以 -31 - (27) (27)583221 外’以實施例2同樣之方法進行。聚合中，未觀測到附著 至反應器。所得之聚苯醚之平均粒徑爲42 β m ^ 1,000 // m以上之粒子並未存在。同實施例1進行各測定且結果 示於表1。 實施例8 除了未改變所使用溶劑之全量且令組成重量比爲正丁 醇：甲醇：二甲苯=85 : H 25 : 〇.75以外，以實施例i 之方法進行。聚合中，並未觀測到附著至反應器。所得之 聚苯醚之平均粒徑爲54 // m、1，000 # m以上之粒子並 未存在。又，同實施例1進行各測定且結果示於表1。 比較例5 根據美國專利62 1 1 3 2 7號說明書實施例記載之方法進 行。即，以溴化銅和二正丁胺做爲觸媒，於甲苯溶劑中， 4 Ot至4 5 t之溫度範圍下，一邊於氧供給下攪拌一邊將2 ，6 -二甲基苯酚聚合，其次停止供給氧氣，於氮氣密封 下將三乙酸胺之水溶液一邊攪拌一邊加入，於水相中萃 取銅觸媒且令溫度爲55°C並於此狀態保持70分鐘。其次 ，將所得之混合物以切斷加壓型之溶液離心分離器分成溶 解聚苯醚之甲苯溶液相、和溶解銅之水相。將甲苯蒸除濃 縮至所得之聚苯醚溶液之固形成分爲65 %爲止，再使用 脫氧擠壓機進行脫氣擠壓，取得九狀之低分子量聚苯醚。 此九狀物之平均粒徑爲1，〇〇〇 # m以上、丨，000 A m以上 -32- (28) 之粒子存在97 wt% 。測定九狀物之7? sp/ c、分子量分 佈、Tg、比介電率。結果示於表i。 實施例9 根據特公昭59 - 23332號公報實施例3記載之方法進 行聚合。即，對溴化銅、溴化氫、N，N · -二一第三丁基 乙二胺、N，N-二甲基—正丁胺和二一正丁胺所構成觸 媒之甲苯溶液，一邊通入氧氣一邊將50重量％之2，6-二甲基苯酚之甲苯溶液歷3 5分鐘加入，74分鐘後停止供 給氧氣。於聚合混合物中加入乙二胺四醋酸三鈉鹽之水溶 液’並將混合物保持於70°C。所得之混合物以切斷加壓 型之溶液離心分離器分成溶解聚苯醚之甲苯溶液相、和溶 解銅之水相。如此處理所得之混合物其後被送至Shear Press公司製離心分離器，取得聚苯醚含量爲26 wt%之 聚苯醚溶液。將此溶液視爲（A )。準備內部具備攪拌渦 輪翼及擋板之附有外套套管之析出槽，將（A )之聚苯醚 溶液以表2條件a所定之份量添加，一邊攪拌一邊於套管 中流過冷媒，並將溫度維持於-1 (TC。將相同調整至溫度 爲- 1 0°C之甲醇僅以表2條件a所定之份量添加。此時， 貧溶劑甲醇與良溶劑甲苯之重量比率爲甲醇/甲苯=2.5 。令液體彼此混合分散，取得析出聚苯醚之流漿後將此混 合物以努采漏斗過濾，並且撒上調整至一 1 〇 °C的甲醇進行 洗淨。其後將所得之濾渣於！4〇t下進行真空乾燥1小時 -33- (29) (29)583221 所得之聚苯醚之平均粒徑爲42 // m、l，〇〇〇 # m以 上之粒子並未存在。同實施例1進行各測定且結果示於表 1 °以貧溶劑甲醇和良溶劑甲苯之重量比率分別爲甲醇/ 甲苯=5.0 (條件^ ) 、7.0 (條件c ) 、1 2 · 0 (條件d )之 比例進行同樣之操作。任一種條件均令聚合物以粒子型 式析出’且不存在1，000 // m以上的粒子。同實施例1進 行各測定且結果示於表1。 實施例1 0 同實施例9，但以析出溫度爲1 °C且實施條件a。任 一種條件均令聚合物以粒子型式析出，且不存在ι，〇〇〇 // m以上的粒子。同實施例1進行各測定且結果示於表1 比較例6 同實施例9，但以析出溫度爲30°C且實施條件a。此 條件爲令析出之聚合物發黏且纒繞至攪拌渦輪翼並呈塊狀 ，不能蓮轉。 -34- (30)583221 表1 實驗編號 η sp/c [dl/g] 產率 [%] 平均粒徑 βπι Mw/Mn Tg [°C] 比介電率 實施例1 0.116 97 56 1.89 185 2.49 實施例2 0.082 98 34 1.87 167 2.52 實施例3 0.075 98 39 1.92 155 2.55 比較例1 0.070 88 15 1.35 135 2.80 比較例2 0.072 76 39 2.56 142 2.71 比較例3 0.476 97 920 2.58 215 2.45 比較例4 0.195 64 850 2.39 205 2.47 實施例4 0.081 98 43 1.85 178 2.48 實施例5 0.079 97 33 2.10 180 2.50 實施例6 0.085 98 54 1.89 169 2.48 實施例7 0.085 98 42 1.87 167 2.53 實施例8 0.103 97 59 1.88 183 2.48 比較例5 0.122 >1000 2.68 162 2.59 實施例9-a 0.120 90 256 1.75 189 2.47 實施例9-b 0.116 92 350 1.82 188 2.47 實施例9-c 0.112 92 625 1.93 185 2.50 實施例9-d 0.112 93 280 2.08 185 2.50 實施例if 0.124 89 430 1.88 189 2.46 比較例6 無法析出 -35- (31)583221 12.析出條件表 條件 a b c d 莖萃醚溶液之重量份 70 40 30 20_ ^之重量份 130 160 170 180 甲轉/甲苯重量比 2.5 5.0 7.0 12.0__Presion LCR Meter CHP—Model 4284A). Example 1 In a reactor of 1.5 liters with a sleeve equipped with a reflux cooler in the bottom of the reactor equipped with a sprayer for introducing oxygen-containing gas, agitating turbine wings and baffles, and a ventilation gas flow line above the reactor, Add 0.2512 g of copper chloride dihydrate, 1.1 062 g of 35% hydrochloric acid, 3.6179 g of di-n-butylamine, 9.5937 g of N, N, N ,, N'-tetramethylpropanediamine, 211.63 g of methanol, and 493.80 g of n- Butanol and 180.0 g of 2,6-dimethylphenol. The composition weight ratio of the solvent was n-butanol: methanol = 70: 30. Next, while vigorously stirring, the reactor was introduced with oxygen at a speed of 180 ml / min from a sprayer, and at the same time, a heating medium was passed into the sleeve to adjust the polymerization temperature to 40 ° C. The polymerization solution immediately appeared as a slurry. During the polymerization, no adhesion to the reactor was observed. 120 minutes after the introduction of oxygen, the oxygen ventilation was stopped, and a 10% aqueous solution of ethylenediamine tetraacetic acid tripotassium salt (a test reagent manufactured by Tongren Chemical Research Institute) was added to the obtained polymerization mixture, and the temperature was maintained at 50. ° C. Next, add a small amount of each of hydroquinone (test reagent manufactured by Wako Pure Chemical Industries, Ltd.) and keep it at 50 ° C until the polyphenylene ether in the form of slurry turns white. After the completion of the filtration, the wet polyphenylene ether of the filter residue was put into a methanol washing solvent containing 50% water, and stirred at 60 ° C. The filtration was continued, and the residue was sprayed with methanol containing 50% water and washed 'to obtain a wet polyphenylene ether. Secondly, the polyphenylene ether was dried by vacuum drying at 110 ° C. Particles with an average particle size of 56 Mm and 10,000 / zm or more do not exist. The Wsp / c, yield, molecular weight distribution, Tg, and specific permittivity were measured as -28- (24) (24) 583221. The results are shown in Table 1. Example 2 was carried out in the same manner as in Example 1 except that the entire amount of the solvent used was not changed and the composition-to-weight ratio was n-butanol: methanol = 30: 70. During the polymerization, no adhesion to the reactor was observed. The obtained polyphenylene ether had an average particle diameter of 34 β m '1,000 // m or more particles did not exist. Each measurement was performed in the same manner as in Example 1. The results are shown in Table 1. Example 3 was carried out in the same manner as in Example 1 except that the total amount of the solvent used was not changed and the composition-to-weight ratio was n-butanol: methanol = 1 0:90. During the polymerization, no adhesion to the reactor was observed. The obtained polyphenylene ether had an average particle diameter of 39 β m ^ 1,000 // m or more particles did not exist. Each measurement was performed in the same manner as in Example 1. The results are shown in Table 1. Comparative Example 1 Except that the total amount of the solvent used was not changed, and the composition-to-weight ratio was n-butanol: methanol = 〇: 1 〇〇, that is, except that the methanol was used as a solvent alone and the polymerization time was 240 minutes, the method of Example 1 was used. . During the polymerization, no adhesion to the reactor was observed. The particles with an average particle size of 15 // m and 1,000 // m or more of the obtained polyphenylene ether did not exist. Each measurement was performed in the same manner as in Example 1. The results are shown in Table 1. -29- (25) (25) 583221 Comparative Example 2 The procedure of Example 1 was performed except that water-saturated n-butanol was used alone as a solvent and the polymerization time was 240 minutes. During the polymerization, no adhesion to the reactor was observed. The average particle size of the obtained polyphenylene ether was 3 9 // m. '1,000 // m or more particles did not exist. Each measurement was performed in the same manner as in Example 1. The results are shown in Table 1. Comparative Example 3 ♦ The method of Example 1 was performed except that the total amount of the solvent used was not changed, and the composition-to-weight ratio was xylene: n-butanol: methanol = 60: 20: 20, and methanol was used as a washing solvent. A large amount of adhesion to the reactor was observed during the polymerization. The average particle size of the obtained polyphenylene ether was 920 // m, and the particles above 1,000 # m were present at 46%. Each measurement was performed in the same manner as in Example 1. The results are shown in Table 1. Comparative Example 4 The procedure of Comparative Example 3 was carried out except that the polymerization time was set at 55 minutes. A large amount of adhesion to the reactor was observed during the polymerization. The average particle size of the obtained polyphenylene ether was 850 / zm, and the particles having a size of 1,000,000 / m or more were present at 38%. Each measurement was performed in the same manner as in Example 1. The results are shown in Table 1. Example 4 Except that 126 g of 2,6-dimethylphenol and 54 g of 2,3,6-trimethylphenol were used as phenol compounds, -30- (26) (26) ) 583221 method. No adhesion to the reactor was observed during the polymerization. The obtained polyphenylene ether had an average particle diameter of 43 # m, and particles of 10,000 / zm or more did not exist. Each measurement was performed in the same manner as in Example 1. The results are shown in Table 1. Example 5 In addition to using 126 g of 2,6-dimethylphenol and 54 g of 2,6-diphenylphenol as phenolic compounds, and 0.1169 g of N, N as the catalyst component, diamine, N ', N'-tetramethylethylenediamine, the polymerization temperature was 60 ° C, and the polymerization time was 180 minutes, except for the same method as in Example 2. No adhesion to the reactor was observed during the polymerization. The particles having an average particle diameter of 33 β m '1,000 or more did not exist. Each measurement was performed in the same manner as in Example 1. The results are shown in Table 1. Example 6 Except that the total amount of the solvent used is not changed, and the composition-to-weight ratio is n-hexanol: methanol = 10: 90, and a solvent composed of methanol: water = 90: 10 weight ratio is used as a cleaning solvent, examples are used 1 method. During the polymerization, no adhesion to the reactor was observed. The particles with an average particle size of 54 // m '1,000 // m or more of the obtained polyphenylene ether did not exist. Each measurement was performed in the same manner as in Example 1. The results are shown in Table 1. Example 7 Except for the phenol compound, 2.5 mol% of 2,6-dimethylphenol containing 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane was used as -31-(27 ) (27) 583221 The procedure was performed in the same manner as in Example 2. During the polymerization, no adhesion to the reactor was observed. The obtained polyphenylene ether had an average particle diameter of 42 β m ^ 1,000 // m or more particles did not exist. Each measurement was performed in the same manner as in Example 1. The results are shown in Table 1. Example 8 was carried out in the same manner as in Example i except that the total amount of the solvent used was not changed and the composition-to-weight ratio was n-butanol: methanol: xylene = 85: H25: 0.75. During the polymerization, no adhesion to the reactor was observed. The average particle size of the obtained polyphenylene ether was 54 // m, and particles of 1,000 # m or more did not exist. Each measurement was performed in the same manner as in Example 1. The results are shown in Table 1. Comparative Example 5 The method described in the example of U.S. Patent No. 62 1 1 3 2 7 was carried out. That is, using copper bromide and di-n-butylamine as catalysts and polymerizing 2,6-dimethylphenol in a toluene solvent at a temperature range of 4 Ot to 4 5 t while stirring under the supply of oxygen, Next, stop the supply of oxygen, and add the aqueous solution of amine triacetate while stirring under a nitrogen seal, and extract the copper catalyst in the water phase to keep the temperature at 55 ° C and keep it in this state for 70 minutes. Next, the obtained mixture was separated into a toluene solution phase in which polyphenylene ether was dissolved and an aqueous phase in which copper was dissolved by a pressure-separated solution centrifugal separator. The toluene was distilled off and concentrated to a solid content of 65% of the obtained polyphenylene ether solution, and then degassed using a deoxidizing extruder to obtain nine-shaped low molecular weight polyphenylene ether. The average particle diameter of this nine-item is 1, 000 # m or more and 1,000 A m or more -32- (28), and 97 wt% of the particles are present. The 7? Sp / c, molecular weight distribution, Tg, and specific permittivity of the nine substances were measured. The results are shown in Table i. Example 9 Polymerization was performed according to the method described in Example 3 of Japanese Patent Publication No. Sho 59-23332. That is, a toluene solution of a catalyst composed of copper bromide, hydrogen bromide, N, N · -di-tert-butylethylenediamine, N, N-dimethyl-n-butylamine, and di-n-butylamine While feeding oxygen, a 50% by weight solution of 2,6-dimethylphenol in toluene was added over 35 minutes, and the supply of oxygen was stopped after 74 minutes. To the polymerization mixture was added an aqueous solution of ethylenediaminetetraacetic acid trisodium salt 'and the mixture was maintained at 70 ° C. The obtained mixture was separated into a toluene solution phase in which polyphenylene ether was dissolved and an aqueous phase in which copper was dissolved by a pressure separator of a pressure-cutting type. The mixture thus treated was then sent to a centrifugal separator manufactured by Shear Press to obtain a polyphenylene ether solution having a polyphenylene ether content of 26 wt%. This solution was regarded as (A). Prepare a precipitation tank with an outer casing and a casing with a stirring turbine wing and baffle inside. Add the polyphenylene ether solution of (A) in the amount specified in Table 2 Condition a, and flow the refrigerant through the casing while stirring. The temperature was maintained at -1 (TC. Methanol adjusted the same to a temperature of -10 ° C was added only in the amount specified in condition a of Table 2. At this time, the weight ratio of lean solvent methanol to good solvent toluene was methanol / toluene = 2.5. The liquids are mixed and dispersed with each other. After obtaining a slurry of the precipitated polyphenylene ether, the mixture is filtered through a hopper funnel, and sprinkled with methanol adjusted to a temperature of 10 ° C to be washed. Thereafter, the obtained filter residue is left over! Vacuum drying at 40 ° C for 1 hour-33- (29) (29) 583221 The average particle size of the polyphenylene ether obtained was 42 // m, and particles with a size of 10,000 # m or more did not exist. Same implementation Example 1 performed each measurement and the results are shown in Table 1. The weight ratios of the lean solvent methanol and the good solvent toluene were methanol / toluene = 5.0 (condition ^), 7.0 (condition c), and 1 2 · 0 (condition d). The same operation is performed. The polymer is precipitated in the form of particles in any condition. There are no particles greater than 1,000 // m. Each measurement was performed in the same manner as in Example 1. The results are shown in Table 1. Example 10 was the same as in Example 9, except that the precipitation temperature was 1 ° C and the condition a was implemented. Under one condition, the polymer was precipitated in a particle form, and there were no particles having a particle size of 100,000 / m or more. Each measurement was performed in the same manner as in Example 1, and the results are shown in Table 1. Comparative Example 6 Same as Example 9, but with precipitation. The temperature is 30 ° C and the condition a is implemented. This condition is to make the precipitated polymer tacky and entangled to the stirring turbine wing and become lumpy, and cannot be turned. -34- (30) 583221 Table 1 Experiment number η sp / c [dl / g] Yield [%] Average particle size βπm Mw / Mn Tg [° C] Specific permittivity Example 1 0.116 97 56 1.89 185 2.49 Example 2 0.082 98 34 1.87 167 2.52 Example 3 0.075 98 39 1.92 155 2.55 Comparative Example 1 0.070 88 15 1.35 135 2.80 Comparative Example 2 0.072 76 39 2.56 142 2.71 Comparative Example 3 0.476 97 920 2.58 215 2.45 Comparative Example 4 0.195 64 850 2.39 205 2.47 Example 4 0.081 98 43 1.85 178 2.48 Implementation Example 5 0.079 97 33 2.10 180 2.50 Example 6 0.085 98 54 1.89 169 2.48 Example 7 0.085 98 42 1.87 167 2.53 Example 8 0.103 97 59 1.88 183 2.48 Comparative Example 5 0.122 > 1000 2.68 162 2.59 Example 9-a 0.120 90 256 1.75 189 2.47 Example 9-b 0.116 92 350 1.82 188 2.47 Example 9- c 0.112 92 625 1.93 185 2.50 Example 9-d 0.112 93 280 2.08 185 2.50 Example if 0.124 89 430 1.88 189 2.46 Comparative Example 6 Unable to precipitate -35- (31) 583221 12. Precipitation conditions Table conditions abcd Stem extract ether solution Parts by weight 70 40 30 20_ ^ Parts by weight 130 160 170 180 Formazan / toluene weight ratio 2.5 5.0 7.0 12.0__
參考例Reference example
使用實施例1、實施例2、實施例3、實施例4、實施 例7、比較例3及比較例5所得之聚苯醚並且觀察對於甲 基乙基酮的溶解度。試驗方法爲如下實施。首先，將1 0 0 克之甲基乙基酮放入圓底燒瓶中，並於2〇 °C下使用磁性 攪拌子進行緩慢攪拌。於此處，將各例之聚苯醚2 0克一 次性添加。除了比較例5之聚苯醚以外之混合物於初期之 混濁幾乎變成澄淸。一次性添加後’測定變成澄淸的時間 (溶解時間）。又，觀測溶解時之燒瓶內部的樣子。結果 示方令表 3 ° -36- (33)583221 及做爲其他樹脂的改質劑。又，根據本發明之方法則可有 效率製造該低分子量聚苯醚。The polyphenylene ethers obtained in Example 1, Example 2, Example 3, Example 4, Example 7, Comparative Example 3, and Comparative Example 5 were used and the solubility in methyl ethyl ketone was observed. The test method was implemented as follows. First, put 100 g of methyl ethyl ketone in a round bottom flask, and stir slowly at 20 ° C using a magnetic stirrer. Here, 20 g of each polyphenylene ether was added once. In the mixture other than the polyphenylene ether of Comparative Example 5, the initial haze became almost clear. After the one-time addition, the time (dissolution time) when it became clear was measured. In addition, the state of the inside of the flask at the time of dissolution was observed. Results Table 3 ° -36- (33) 583221 and modifier for other resins. In addition, the method according to the present invention can efficiently produce the low molecular weight polyphenylene ether.
-38--38-
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| JP2002063626A JP4007828B2 (en) | 2002-03-08 | 2002-03-08 | Method for producing low molecular weight polyphenylene ether |
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Families Citing this family (38)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7235192B2 (en) | 1999-12-01 | 2007-06-26 | General Electric Company | Capped poly(arylene ether) composition and method |
| US6384176B1 (en) | 2000-07-10 | 2002-05-07 | General Electric Co. | Composition and process for the manufacture of functionalized polyphenylene ether resins |
| US6878781B2 (en) | 2001-03-27 | 2005-04-12 | General Electric | Poly(arylene ether)-containing thermoset composition in powder form, method for the preparation thereof, and articles derived therefrom |
| JP4471073B2 (en) * | 2003-07-02 | 2010-06-02 | 三菱瓦斯化学株式会社 | Method for producing bifunctional phenylene ether oligomer |
| US7148296B2 (en) * | 2003-10-03 | 2006-12-12 | General Electric Company | Capped poly(arylene ether) composition and process |
| US7151158B2 (en) | 2004-01-30 | 2006-12-19 | General Electric Company | Method of preparing a poly(arylene ether), apparatus therefor, and poly(arylene ether) prepared thereby |
| US20080070096A1 (en) * | 2004-08-09 | 2008-03-20 | Ionescu Lucia D | Proton Conducting Copolymers |
| US20070004871A1 (en) * | 2005-06-30 | 2007-01-04 | Qiwei Lu | Curable composition and method |
| US7378455B2 (en) * | 2005-06-30 | 2008-05-27 | General Electric Company | Molding composition and method, and molded article |
| US7429800B2 (en) * | 2005-06-30 | 2008-09-30 | Sabic Innovative Plastics Ip B.V. | Molding composition and method, and molded article |
| US20070106051A1 (en) * | 2005-11-10 | 2007-05-10 | Alvaro Carrillo | Polyfunctional poly(arylene ether) method |
| US7541421B2 (en) * | 2005-12-08 | 2009-06-02 | Sabic Innovative Plastics Ip B.V. | Poly(arylene ether) copolymer |
| JP4988218B2 (en) * | 2006-02-13 | 2012-08-01 | 株式会社日立製作所 | Manufacturing method of low dielectric loss resin |
| JP5099805B2 (en) * | 2006-03-10 | 2012-12-19 | 旭化成ケミカルズ株式会社 | Process for producing polyphenylene ether having two peaks of molecular weight distribution |
| US7439310B2 (en) | 2006-07-06 | 2008-10-21 | Asahi Kasei Chemicals Corporation | Polyphenylene ether modified by reaction with cresol novolac epoxy resin |
| US7638566B2 (en) | 2006-10-30 | 2009-12-29 | Sabic Innovative Plastics Ip B.V. | Poly(arylene ether) compositions |
| US7655278B2 (en) * | 2007-01-30 | 2010-02-02 | Sabic Innovative Plastics Ip B.V. | Composite-forming method, composites formed thereby, and printed circuit boards incorporating them |
| US8075812B2 (en) * | 2007-04-04 | 2011-12-13 | Sabic Innovative Plastics Ip B.V. | Method of separating a poly(arylene ether) composition from a solvent, and poly(arylene ether) composition prepared thereby |
| JP5390128B2 (en) * | 2008-06-20 | 2014-01-15 | 株式会社カネカ | Method for producing low molecular weight poly (2,6-diarylphenylene ether) |
| US8642719B2 (en) * | 2011-02-28 | 2014-02-04 | Corning Incorporated | Solvent mixture for molecular weight control |
| US8901544B2 (en) | 2011-12-06 | 2014-12-02 | Corning Incorporated | Organic thin film transistor with ion exchanged glass substrate |
| JP5759087B2 (en) * | 2012-04-25 | 2015-08-05 | サビック グローバル テクノロジーズ ベスローテン フェンノートシャップ | Poly (phenylene ether) copolymer and production method |
| US8703848B1 (en) * | 2012-10-09 | 2014-04-22 | Sabic Innovative Plastics | Blends of micronized polyphenylene ether and thermoplastic polyurethanes blend |
| US9455067B2 (en) | 2013-03-18 | 2016-09-27 | Iteq Corporation | Low dielectric materials |
| US9257212B2 (en) * | 2013-03-18 | 2016-02-09 | Iteq Corporation | Dielectric material with low dielectric loss |
| EP2799465A1 (en) * | 2013-04-29 | 2014-11-05 | Evonik Industries AG | Method for the purification of poly(arylene ethers) |
| US20150028247A1 (en) | 2013-07-23 | 2015-01-29 | Sabic Innovative Plastics Ip B.V. | Rigid foam and associated article and method |
| US9175160B2 (en) | 2013-08-28 | 2015-11-03 | Sabic Global Technologies B.V. | Blend of poly(phenylene ether) particles and polyoxymethylene, article thereof, and method of preparation |
| US9447227B2 (en) | 2013-10-03 | 2016-09-20 | Sabic Global Technologies B.V. | Flexible polyurethane foam and associated method and article |
| US9074086B1 (en) * | 2013-12-18 | 2015-07-07 | Sabic Global Technologies B.V. | Polyolefin composition with poly(phenylene ether) filler and article thereof |
| TWI548453B (en) | 2014-12-05 | 2016-09-11 | 財團法人工業技術研究院 | Aqueous-phase catalyst compositions and method for preparing polyphenylene ether |
| WO2016200791A1 (en) * | 2015-06-09 | 2016-12-15 | Sabic Global Technologies B.V. | Method for poly(phenylene ether) manufacture and associated poly(phenylene ether) |
| CN109971154A (en) * | 2016-03-23 | 2019-07-05 | 联茂(无锡)电子科技有限公司 | Dielectric materials |
| WO2018194797A1 (en) | 2017-04-21 | 2018-10-25 | Sabic Global Technologies B.V. | Poly(phenylene ether) copolymer compositions and associated methods and articles |
| WO2018194798A1 (en) | 2017-04-21 | 2018-10-25 | Sabic Global Technologies B.V. | Poly(phenylene ether) copolymer process and compositions |
| JP2021014556A (en) * | 2019-07-16 | 2021-02-12 | 旭化成株式会社 | Production method of polyphenylene ether resin |
| CN110804174B (en) * | 2019-12-06 | 2022-07-08 | 中国科学院大连化学物理研究所 | Supported catalyst and application thereof in preparation of low-molecular-weight hydroxyl-terminated polyphenyl ether |
| CN116867835A (en) * | 2021-01-25 | 2023-10-10 | 旭化成株式会社 | Polyphenylene ether, method for producing the same, heat-curable composition, prepreg, and laminate |
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| JPS4926919A (en) | 1972-07-08 | 1974-03-09 | ||
| US4463164A (en) * | 1983-02-15 | 1984-07-31 | Borg-Warner Chemicals, Inc. | Process for preparing polyphenylene ethers |
| DE3529093A1 (en) * | 1985-08-14 | 1987-02-19 | Bayer Ag | METHOD FOR THE PRODUCTION OF MONO- AND BIFUNCTIONAL OLIGOPHENYLENE OXIDES |
| EP1152948A4 (en) * | 1999-01-19 | 2003-02-12 | Volusia Holding Corp | Labeler for pipes, conduits, tubes, and rods |
| US6211327B1 (en) | 1999-02-05 | 2001-04-03 | General Electric Company | Process for the manufacture of low molecular weight polyphenylene ether resins |
| JP4314666B2 (en) * | 1999-03-29 | 2009-08-19 | 三菱瓦斯化学株式会社 | Method for producing low viscosity polyphenylene ether |
| JP4736254B2 (en) * | 2001-06-28 | 2011-07-27 | 三菱瓦斯化学株式会社 | Bifunctional phenylene ether oligomer and its production method |
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| JP4007828B2 (en) | 2007-11-14 |
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